Polymer-based film with balanced properties

ABSTRACT

A film includes 20.0 weight percent to 69.5 weight percent of a linear low density polyethylene (LLDPE) based polymer. The LLDPE having a high density fraction (HDF) from 3.0% to 8.0%, an I10/I2 ratio from 5.5 to 6.9, and a short chain branching distribution (SCBD) of less than or equal to 8.0° C. The film also includes 0.0 weight percent to 10.0 weight percent low density polyethylene (LDPE) based polymer, and 30.0 weight percent to 70.0 weight percent pore former.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application Ser.No. 62/773,468 filed on Nov. 30, 2018, the entire disclosure of which ishereby incorporated by reference.

TECHNICAL FIELD

Embodiments of the present disclosure generally relate to breathablebacksheets with balanced properties made from ethylene-based polymershaving high density fractions.

BACKGROUND

Polymer-based films may be used in end products, such as, for example,as backsheets for use in products, such as, for example, diapers,hygienic pads, bandages, etc. Such films are generally made from amixture of linear low density polyethylene (LLDPE), low densitypolyethylene (LDPE), and one or more fillers, such as, for example,calcium carbonate (CaCO₃). These polymer-based films are formulated witha focus on several properties that are indicative of the performance ofthe backsheets in which they may be incorporated. Among these propertiesare the water vapor transmission rate (WVTR), the hydrostatic pressure,the tear resistance, the noise and the secant modulus. It is difficultto form polymer-based films having a good balance of all theseproperties because when one of these properties is increased, one ormore of these properties generally decrease.

SUMMARY

Therefore, as competition increases in the breathable backsheetindustry, producers of ethylene-based polymers strive to make theirproducts with broader ranges of properties, which in turn result inproducts, such as, for example, breathable backsheets, that haveimproved balance of properties. As such, ongoing needs exist forprocesses that are capable of producing ethylene-based polymers having awider array of properties, such as, for example, high density fractions,so that these ethylene-based polymers may be used to provide an improvedbalance of properties in products, such as, for example, breathablebacksheets. It has been found that by controlling the location of thecatalyst inlet, such that it is upstream from a first reactor anddownstream from a second reactor, reactions of components in thepresence of the catalyst can better be controlled when forming anethylene-based polymer. Further, because the catalyst is being combinedwith the components in a flow restricted area, compared to a bulk of areactor, the catalyst and the components sufficiently mix before theyreach the second reactor, and the second reactor can be non-agitatedreactor, which reduces costs and energy consumption.

Accordingly, embodiments of the present disclosure are directed tobreathable backsheets made with ethylene-based polymers.

Embodiments of the present disclosure are directed to a film comprising:20.0 weight percent to 69.5 weight percent linear low densitypolyethylene (LLDPE) based polymer, wherein the LLDPE based polymercomprises a high density fraction (HDF) from 3.0% to 10.0%, wherein thehigh density fraction is measured by crystallization elutionfractionation (CEF) integration at temperatures from 93° C. to 119° C.,an I₁₀/I₂ ratio from 5.5 to 6.9, wherein 12 is the melt index whenmeasured according to ASTM D 1238 at a load of 2.16 kg and temperatureof 190° C. and I₁₀ is the melt index when measured according to ASTM D1238 at a load of 10 kg and temperature of 190° C., and a short chainbranching distribution (SCBD) of less than or equal to 8.0° C., whereinthe short chain branching distribution is measured by CEF full width athalf height; 0.0 weight percent to 10.0 weight percent low densitypolyethylene (LDPE) based polymer; and 30.0 weight percent to 70.0weight percent pore former.

Additional features and advantages will be set forth in the detaileddescription which follows, and in part will be readily apparent to thoseskilled in the art from that description or recognized by practicing theembodiments described herein, including the detailed description whichfollows, the claims, as well as the appended drawing.

It is to be understood that both the foregoing general description andthe following detailed description describe various embodiments and areintended to provide an overview or framework for understanding thenature and character of the claimed subject matter. The accompanyingdrawing is included to provide a further understanding of the variousembodiments, and is incorporated into and constitutes a part of thisspecification. The drawing illustrates the various embodiments describedherein, and together with the description serve to explain theprinciples and operations of the claimed subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically depicts a system for producing ethylene-basedpolymers having high density fractions according to embodimentsdisclosed and described herein;

FIG. 2 graphically depicts the properties of films of Example 1, whichwas produced according to embodiments disclosed and described herein,and Comparative Examples 1-5;

FIG. 3A and FIG. 3B are schematics of a test set-up to measure noiseaccording to embodiments disclosed and described herein.

DETAILED DESCRIPTION

Specific embodiments of the present application will now be described.The disclosure may, however, be embodied in different forms and shouldnot be construed as limited to the embodiments set forth in thisdisclosure. Rather, these embodiments are provided so that thisdisclosure will be thorough and complete, and will fully convey thescope of the subject matter to those skilled in the art.

According to one embodiment, a film comprises: 20.0 weight percent to69.5 weight percent linear low density polyethylene (LLDPE) basedpolymer, wherein the LLDPE based polymer comprises a high densityfraction (HDF) from 3.0% to 10.0%, wherein the high density fraction ismeasured by crystallization elution fractionation (CEF) integration attemperatures from 93° C. to 119° C., an I₁₀/I₂ ratio from 5.5 to 6.9,wherein 12 is the melt index when measured according to ASTM D 1238 at aload of 2.16 kg and temperature of 190° C. and ho is the melt index whenmeasured according to ASTM D 1238 at a load of 10 kg and temperature of190° C., and a short chain branching distribution (SCBD) of less than orequal to 8.0° C., wherein the short chain branching distribution ismeasured by CEF full width at half height; 0.0 weight percent to 10.0weight percent low density polyethylene (LDPE) based polymer; and 30.0weight percent to 70.0 weight percent pore former.

Definitions

The term “polymer” refers to a polymeric compound prepared bypolymerizing monomers, whether of the same or a different type. Thegeneric term polymer thus embraces the term “homopolymer,” usuallyemployed to refer to polymers prepared from only one type of monomer aswell as “copolymer” which refers to polymers prepared from two or moredifferent monomers. The term “interpolymer,” as used herein, refers to apolymer prepared by the polymerization of at least two different typesof monomers. The generic term interpolymer thus includes copolymers, andpolymers prepared from more than two different types of monomers, suchas terpolymers.

As used herein, the “solution polymerization reactor” is a vessel, whichperforms solution polymerization, wherein ethylene monomer and at leastC₃-C₁₂ α-olefin comonomer copolymerize after being dissolved in anon-reactive solvent that contains a catalyst. In the solutionpolymerization process, hydrogen may be utilized; however, it is notrequired in all solution polymerization processes.

“Polyethylene” or “ethylene-based polymer” shall mean polymerscomprising greater than 50% by mole of units derived from ethylenemonomer. This includes ethylene-based homopolymers or copolymers(meaning units derived from two or more comonomers). Common forms ofpolyethylene known in the art include, but are not limited to, LowDensity Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE);Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene(VLDPE); single-site catalyzed Linear Low Density Polyethylene,including both linear and substantially linear low density resins(m-LLDPE); Medium Density Polyethylene (MDPE); and High DensityPolyethylene (HDPE).

The term “LDPE” may also be referred to as “high pressure ethylenepolymer” or “highly branched polyethylene” and is defined to mean thatthe polymer is partly or entirely homopolymerized or copolymerized inautoclave or tubular reactors at pressures above 14,500 psi (100 MPa)with the use of free-radical initiators, such as peroxides (see, forexample, U.S. Pat. No. 4,599,392, which is hereby incorporated byreference in its entirety). LDPE resins typically have a density in therange of 0.916 to 0.940 g/cm.

The term “LLDPE”, includes resin made using Ziegler-Natta catalystsystems as well as resin made using single-site catalysts, including,but not limited to, bis-metallocene catalysts (sometimes referred to as“m-LLDPE”), phosphinimine, and constrained geometry catalysts; and resinmade using post-metallocene, molecular catalysts, including, but notlimited to, bis(biphenylphenoxy) catalysts (also referred to aspolyvalent aryloxyether catalysts). LLDPE includes linear, substantiallylinear, or heterogeneous ethylene-based copolymers or homopolymers.LLDPEs contain less long chain branching than LDPEs and include thesubstantially linear ethylene polymers, which are further defined inU.S. Pat. Nos. 5,272,236; 5,278,272; 5,582,923; and 5,733,155; thehomogeneously branched ethylene polymers such as those in U.S. Pat. No.3,645,992; the heterogeneously branched ethylene polymers such as thoseprepared according to the process disclosed in U.S. Pat. No. 4,076,698;and blends thereof (such as those disclosed in U.S. Pat. No. 3,914,342or 5,854,045). The LLDPE resins can be made via gas-phase,solution-phase or slurry polymerization or any combination thereof,using any type of reactor or reactor configuration known in the art.

The term “procatalyst” refers to a compound that has catalytic activitywhen combined with an activator. The term “activator” refers to acompound that chemically reacts with a procatalyst in a manner thatconverts the procatalyst to a catalytically active catalyst. As usedherein, the terms “cocatalyst” and “activator” are interchangeableterms.

The term “non-agitated reactor” refers to a reactor that does notinclude mechanical agitation, such as agitation by a stirrer, a mixer, akneader, or the like. Examples of non-agitated reactors include plugflow reactors, tank reactors, and loop reactors, all without stirrers,mixers, or the like.

The term “mixer” refers to an apparatus that mechanically mixes thecomponents present in the apparatus. Examples of mixers include staticmixers, flow shapers, and vessels comprising a stirrer, mixer, kneader,or the like. In embodiments, components present in the mixer—such asmonomers, comonomer, etc.—will react in the mixer.

System Configuration

Reference will now be made in detail to systems for producingethylene-based polymers having high density fractions according toembodiments disclosed and described herein.

With reference now to FIG. 1, a system 100 for producing ethylene-basedpolymer having a high density fraction according to embodimentscomprises a first reactor 110 and a second reactor 120 fluidly connectedto the first reactor 110. The type of reactors used for the firstreactor 110 and the second reactor 120 are not limited and, inembodiments, are reactors suitable for use as solution polymerizationreactors. In embodiments, the first reactor 110 is an agitated solutionpolymerization reactor, such as, for example a loop reactor, anisothermal reactor, an adiabatic reactor, and a continuous stirred tankreactor in parallel, series, and any combinations thereof. The secondreactor 120, according to embodiments, is a non-agitated solutionpolymerization reactor, such as, for example, a non-agitated tankreactor or a tubular reactor (e.g., a plug flow reactor, a piston flowreactor, etc.).

According to embodiments, one or more mixers 130 are positioneddownstream from a first reactor 110 and upstream from a second reactor120. Although FIG. 1 only depicts one mixer, it should be understoodthat additional mixers may be positioned in series or paralleldownstream from the first reactor 110 and upstream from the secondreactor 120. The mixer 130 may be a flow shaper or static mixer. Forexample, in some embodiments, mixer 130 may comprise a flow shaper and astatic mixer. A “flow shaper” as used herein may be any type ofapparatus that alters the flow of a component stream, such as, forexample, a tapered pipe, a diffuser, or a nozzle. In embodiments, suchas the embodiment depicted in FIG. 1, the mixer 130 and the non-agitatedrector 120 may be separate physical apparatuses. However, in someembodiments, the mixer 130 and the non-agitated reactor 120 may be asingle physical apparatus with two distinct zones. As an example, inembodiments, the mixer 130 and non-agitated reactor 120 may both behoused in an elongated tube. In static mixer may be positioned in afirst portion of the elongated tube, while a second portion of theelongated tube does not include the static mixer—or any other type ofagitator. In such an embodiment, the first zone of the elongated tubewhere the static mixer is present is the mixer 130 and the second zoneof the elongated tube where no agitator is present is the non-agitatedreactor 120. In such an embodiment, the mixer 130 and the non-agitatedreactor are housed in a single physical apparatus.

As shown in the embodiment depicted in FIG. 1, the first reactor 110 isconfigured to receive: feed stream 101 that comprises ethylene monomerand C₃-C₁₂ α-olefin comonomer in solvent; first catalyst stream 103;and, optionally, hydrogen (H₂) stream 102. The components of feed stream101, first catalyst stream 103, and optional hydrogen stream 102 arereacted in the first reactor 110 to produce a first polymer fraction.This first polymer fraction is outputted from the first reactor 110 aseffluent 111 a. In embodiments, effluent 111 a comprises unreactedethylene monomer and unreacted C₃-C₁₂ α-olefin comonomer in addition tothe first polymer fraction. It should be understood that, in someembodiments, the components of the feed stream 101 may be added to thefirst reactor 110 together or as separate streams. For example, ethylenemonomer and solvent may be added to the first reactor as a separatestream from the C₃-C₁₂ α-olefin comonomer. The order at which theethylene monomer, C₃-C₁₂ α-olefin comonomer, and solvent into the firstreactor 110 is not limited.

With reference still to FIG. 1, second catalyst stream 112 is added tothe effluent 111 a downstream of the first reactor 110 (i.e., agitatedsolution polymerization reactor) and upstream from the second reactor120 (i.e., non-agitated solution polymerization reactor). The secondcatalyst stream 112 may, in embodiments be added into the mixer 130. Inother embodiments, the second catalyst stream 112 may be addedimmediately before the mixer 130. Second catalyst stream 112 comprises adifferent catalyst than the first catalyst stream 103 and facilitatesreaction of unreacted ethylene monomer and unreacted C₃-C₁₂ α-olefincomonomer present in the effluent 111 a to produce a second polymerfraction. In embodiments, the second polymer fraction has a density andmelt index (I₂) that differ from the density and melt index (I₂) of thefirst polymer fraction. The modified effluent 111 b, which comprises thefirst polymer fraction, the second polymer fraction, and secondcatalyst, is passed from the mixer 130 to the second reactor 120.

A second feed stream 121 comprising additional ethylene monomer,additional C₃-C₁₂ α-olefin comonomer, and solvent is passed to secondreactor 120. The additional ethylene monomer and additional C₃-C₁₂α-olefin comonomer from the second feed stream 121 react in the presenceof the second catalyst introduced into the second reactor 120 via themodified effluent 111 b to form additional second polymer fraction.Accordingly, an ethylene-based polymer, which comprises first polymerfraction and second polymer fraction is outputted from the secondreactor 120 in product stream 122.

By introducing the second catalyst stream 112 downstream from the firstreactor 110 and upstream from the second reactor 120, the secondcatalyst stream 112 mixes with unreacted ethylene monomer and unreactedC₃-C₁₂ α-olefin comonomer present in effluent 111 a prior introductionof second catalyst into the second reactor 120. This circumvents acommon issue that occurs when second catalyst is introduced directlyinto the second reactor 120; gumming of the second catalyst inlet thatundesirably restricts the amount of second catalyst that is added to thesecond reactor 120. Accordingly, by provided the second catalyst stream112 downstream from the first reactor 110 and upstream from the secondreactor 120, agitation is not required in the second reactor 120, whichcan reduce equipment and operating costs. A mixer 130 mixes the secondcatalyst stream 112 with unreacted ethylene monomer and unreacted C₃-C₁₂α-olefin comonomer present in effluent 111 a prior to passing effluent111 a and the second catalyst stream 112 to the second reactor 120. Themixing of unreacted ethylene monomer and unreacted C₃-C₁₂ α-olefincomonomer in the mixer 130 in the presence of second catalyst allows forreactions of the unreacted ethylene monomer and unreacted C₃-C₁₂α-olefin comonomer at low temperatures and high ethylene monomerconcentrations, which results in a second polymer fraction with highdensity, portions to be formed in the mixer 130.

Additionally, in some embodiments, additional ethylene monomer may beadded downstream from the first reactor 110 and upstream from the secondreactor 120, such as, for example, into the mixer 130, to facilitateformation of the second polymer fraction before modified effluent 111 benters the second reactor 120. In some embodiments, the additionalethylene monomer may be added to effluent 111 a (i.e., before the secondcatalyst stream 112 is introduced into the mixer 130), and in otherembodiments, the additional ethylene monomer may be added to the mixer130.

Methods and Components

Reference will now be made in detail to methods and components used insystems of embodiments disclosed above for producing ethylene-basedpolymers having high density fraction according to embodiments disclosedand described herein.

As disclosed previously herein, and with reference to FIG. 1, the firstreactor 110, which is an agitated solution polymerization reactor,receives feed stream 101, first catalyst stream 103, and, optionally,hydrogen stream 102. The components of the feed stream 101—optionallywith hydrogen from hydrogen stream 102—react in the presence of a firstcatalyst, which is introduced into the first reactor 110 via firstcatalyst stream 103, to form a first polymer fraction. The first polymerfraction and non-reacted components exit the first reactor 110 viaeffluent 111 a. Each of these streams and the reaction conditions withinthe first reactor 110 are described in more detail below.

Feed stream 101 comprises ethylene monomer and C₃-C₁₂ α-olefin comonomerin solvent. In some embodiments, the comonomer is C₃-C₈ α-olefin.Exemplary α-olefin comonomers include, but are not limited to,propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, and 4-methyl-1-pentene. The one or more α-olefin comonomersmay, in embodiments, be selected from the group consisting of propylene,1-butene, 1-hexene, and 1-octene. The solvent present in the feed streammay, in embodiments, be aromatic and paraffin solvents. In someembodiments, the solvent may be isoparaffins, such as, for example,ISOPAR E manufactured by ExxonMobil Chemical.

The hydrogen stream 102 is essentially pure hydrogen and, inembodiments, comprises greater than 97 volume percent (vol. %) hydrogen,such as greater than 98 vol. % hydrogen, or greater than 99 vol. %hydrogen.

The first catalyst is added to the first reactor 110 via first catalyststream 103 and facilitates reactions between ethylene monomer, C₃-C₁₂α-olefin comonomer, and, optionally, hydrogen. Catalysts that may beused in embodiments include, but are not limited to, a post-metallocenecatalyst, a constrained geometry complex (CGC) catalyst, a phosphiniminecatalyst, or a bis(biphenylphenoxy) catalyst. Details and examples ofCGC catalysts are provided in U.S. Pat. Nos. 5,272,236; 5,278,272;6,812,289; and WO Publication 93/08221, which are all incorporatedherein by reference in their entirety. Details and examples ofbis(biphenylphenoxy) catalysts are provided in U.S. Pat. Nos. 6,869,904;7,030,256; 8,101,696; 8,058,373; 9,029,487, which are all incorporatedherein by reference in their entirety. In embodiments, the firstcatalyst may be a molecular catalyst including, but not limited to,bis(biphenylphenoxy) catalysts (also referred to as polyvalentaryloxyether catalysts).

Bis(biphenylphenoxy) catalysts are multi-component catalyst systemscomprising a bis(biphenylphenoxy) procatalyst, a cocatalyst thatactivates the procatalyst, as well as other optional ingredients. Inembodiments, the bis(biphenylphenoxy) procatalyst may include ametal-ligand complex according to Formula (I):

In Formula (I), M is a metal chosen from titanium, zirconium, orhafnium, the metal being in a formal oxidation state of +2, +3, or +4; nis 0, 1, or 2; when n is 1, X is a monodentate ligand or a bidentateligand; when n is 2, each X is a monodentate ligand and is the same ordifferent; the metal-ligand complex is overall charge-neutral; O is O(an oxygen atom); each Z is independently chosen from —O—, —S—,—N(R^(N))—, or —P(R^(P))—; L is (C₁-C₄₀)hydrocarbylene or(C₁-C₄₀)heterohydrocarbylene, wherein the (C₁-C₄₀)hydrocarbylene has aportion that comprises a 1-carbon atom to 10-carbon atom linker backbonelinking the two Z groups in Formula (I) (to which L is bonded) or the(C₁-C₄₀)heterohydrocarbylene has a portion that comprises a 1-atom to10-atom linker backbone linking the two Z groups in Formula (I), whereineach of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone ofthe (C₁-C₄₀)heterohydrocarbylene independently is a carbon atom orheteroatom, wherein each heteroatom independently is O, S, S(O), S(O)₂,Si(R^(C))₂, Ge(R^(C))₂, P(R^(C)), or N(R^(C)), wherein independentlyeach R^(C) is (C₁-C₃₀)hydrocarbyl or (C₁-C₃₀)heterohydrocarbyl; R¹ andR⁸ are independently selected from the group consisting of(C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃,—Ge(R^(C))₃, —P(R^(P))₂, —N(R^(N))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃,R^(C)S(O)—, R^(C)S(O)₂—, (R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—,R^(C)C(O)N(R^(N))—, (R^(N))₂NC(O)—, halogen, and radicals having Formula(II), Formula (III), or Formula (IV):

In Formulas (II), (III), and (IV), each of R³¹⁻³⁵, R⁴¹⁻⁴⁸, or R⁵¹⁻⁵⁹ isindependently chosen from (C₁-C₄₀)hydrocarbyl,(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(P))₂,—N(R^(N))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, R^(C)S(O)—, R^(C)S(O)₂—,(R^(C))₂C═N—, R^(C)C(O)O—, R^(C)OC(O)—, R^(C)C(O)N(R^(N))—,(R^(N))₂NC(O)—, halogen, or —H, provided at least one of R¹ or R⁸ is aradical having Formula (II), Formula (III), or Formula (IV).

In Formula (I), each of R²⁻⁴, R⁵⁻⁷, and R⁹⁻¹⁶ is independently selectedfrom (C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃,—Ge(R^(C))₃, —P(R^(P))₂, —N(R^(N))₂—OR^(C), —SR^(C), —NO₂, —CN, —CF₃,R^(C)S(O)—, R^(C)S(O)₂—, (R^(C))₂C═N, R^(C)C(O)O—, R^(C)OC(O)—,R^(C)C(O)N(R^(N))—, (R^(C))₂NC(O)—, halogen, and —H.

Detailed embodiments of various functional groups that can be present inthe compositions depicted in Formulae (I)-(IV) will now be described indetail. It should be understood that the following functional groups areexemplary and are disclosed to provide non-limiting examples of thebis(biphenylphenoxy) procatalyst that can be used according toembodiments.

“Independently selected” as used herein indicates that the R groups,such as, R¹, R², R³, R⁴, and R⁵ can be identical or different (e.g., R¹,R², R³, R⁴, and R⁵ may all be substituted alkyls or R¹ and R² may be asubstituted alkyl and R³ may be an aryl, etc.). Use of the singularincludes use of the plural and vice versa (e.g., a hexane solvent,includes hexanes). A named R group will generally have the structurethat is recognized in the art as corresponding to R groups having thatname. These definitions are intended to supplement and illustrate, notpreclude, the definitions known to those of skill in the art.

When used to describe certain carbon atom-containing chemical groups, aparenthetical expression having the form “(C_(x)-C_(y))” or anon-parenthetical expression having the form “C_(x)-C_(y)” means thatthe unsubstituted form of the chemical group has from x carbon atoms toy carbon atoms, inclusive of x and y. For example, a (C₁-C₄₀)alkyl is analkyl group having from 1 to 40 carbon atoms in its unsubstituted form.In some embodiments and general structures, certain chemical groups maybe substituted by one or more substituents such as R^(S). An R^(S)substituted version of a chemical group defined using the“(C_(x)-C_(y))” parenthetical or “C_(x)-C_(y)” non-parenthetical maycontain more than y carbon atoms depending on the identity of any groupsR¹⁻⁵. For example, a “(C₁-C₄₀)alkyl substituted with exactly one groupR^(S), where R^(S) is phenyl (—C₆H₅)” may contain from 7 to 46 carbonatoms. Thus, in general when a chemical group defined using the“(C_(x)-C_(y))” parenthetical C_(x)-C_(y)” non-parenthetical issubstituted by one or more carbon atom-containing substituents R^(S),the minimum and maximum total number of carbon atoms of the chemicalgroup is determined by adding to both x and y the combined sum of thenumber of carbon atoms from all of the carbon atom-containingsubstituents R^(S).

In some embodiments, each of the chemical groups (e.g., X, R, etc.) ofthe metal-ligand complex of Formula (I) may be unsubstituted having noR^(S) substituents. In other embodiments, at least one of the chemicalgroups of the metal-ligand complex of Formula (I) may independentlycontain one or more than one R^(S). In some embodiments, the sum totalof R^(S) in the chemical groups of the metal-ligand complex of Formula(I) does not exceed 20. In other embodiments, the sum total of R^(S) inthe chemical groups does not exceed 10. For example, if each R¹⁻⁵ wassubstituted with two R^(S), then X and Z cannot be substituted with anR^(S). In another embodiment, the sum total of R^(S) in the chemicalgroups of the metal-ligand complex of Formula (I) may not exceed 5R^(S). When two or more than two R^(S) are bonded to a same chemicalgroup of the metal-ligand complex of Formula (I), each R^(S) isindependently bonded to the same or different carbon atom or heteroatomand may include persubstitution of the chemical group.

“Substitution” as used herein means that at least one hydrogen atom (—H)bonded to a carbon atom or heteroatom of a corresponding unsubstitutedcompound or functional group is replaced by a substituent (e.g., R^(S)).The term “persubstitution” as used herein means that every hydrogen atom(H) bonded to a carbon atom or heteroatom of a correspondingunsubstituted compound or functional group is replaced by a substituent(e.g., R^(S)). The term “polysubstitution” as used herein means that atleast two, but fewer than all, hydrogen atoms bonded to carbon atoms orheteroatoms of a corresponding unsubstituted compound or functionalgroup are replaced by a substituent.

As used herein, “—H” means a hydrogen or hydrogen radical that iscovalently bonded to another atom. “Hydrogen” and “—H” areinterchangeable, and unless clearly specified mean the same thing.

“(C₁-C₄₀)hydrocarbyl” as used herein means a hydrocarbon radical of from1 to 40 carbon atoms and the term “(C₁-C₄₀)hydrocarbylene” means ahydrocarbon diradical of from 1 to 40 carbon atoms, in which eachhydrocarbon radical and each hydrocarbon diradical is aromatic ornon-aromatic, saturated or unsaturated, straight chain or branchedchain, cyclic (including mono- and poly-cyclic, fused and non-fusedpolycyclic, including bicyclic; 3 carbon atoms or more) or acyclic andis unsubstituted or substituted by one or more R^(S).

As used in this disclosure, a (C₁-C₄₀)hydrocarbyl can be anunsubstituted or substituted (C₁-C₄₀)alkyl, (C₃-C₄₀)cycloalkyl,(C₃-C₂₀)cycloalkyl-(C₁-C₂₀)alkylene, (C₆-C₄₀)aryl, or(C₆-C₂₀)aryl-(C₁-C₂₀)alkylene. In some embodiments, each of theaforementioned (C₁-C₄₀)hydrocarbyl groups has a maximum of 20 carbonatoms (i.e., (C₁-C₂₀)hydrocarbyl) and other embodiments, a maximum of 12carbon atoms.

“(C₁-C₄₀)alkyl” and “(C₁-C₁₈)alkyl” as used herein mean a saturatedstraight or branched hydrocarbon radical of from 1 to 40 carbon atoms orfrom 1 to 18 carbon atoms, respectively, which is unsubstituted orsubstituted by one or more R^(S). Examples of unsubstituted(C₁-C₄₀)alkyl are unsubstituted (C₁-C₂₀)alkyl; unsubstituted(C₁-C₁₀)alkyl; unsubstituted (C₁-C₅)alkyl; methyl; ethyl; 1-propyl;2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl;1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Examples of substituted(C₁-C₄₀)alkyl are substituted (C₁-C₂₀)alkyl, substituted (C₁-C₁₀)alkyl,trifluoromethyl, and [C₄₅]alkyl. The term “[C₄₅]alkyl” (with squarebrackets) as used herein means there is a maximum of 45 carbon atoms inthe radical, including substituents, and is, for example, a(C₂₇-C₄₀)alkyl substituted by one R^(S), which is a (C₁-C₅)alkyl,respectively. Each (C₁-C₅)alkyl may be methyl, trifluoromethyl, ethyl,1-propyl, 1-methylethyl, or 1,1-dimethyl ethyl.

“(C₆-C₄₀)aryl” as used herein means an unsubstituted or substituted (byone or more R^(S)) mono-, bi- or tricyclic aromatic hydrocarbon radicalof from 6 to 40 carbon atoms, of which at least from 6 to 14 of thecarbon atoms are aromatic ring carbon atoms, and the mono-, bi- ortricyclic radical comprises 1, 2, or 3 rings, respectively; wherein the1 ring is aromatic and the 2 or 3 rings independently are fused ornon-fused and at least one of the 2 or 3 rings is aromatic. Examples ofunsubstituted (C₆-C₄₀)aryl are unsubstituted (C₆-C₂₀)aryl unsubstituted(C₆-C₁₈)aryl; 2-(C₁-C₅)alkyl-phenyl; 2,4-bis(C₁-C₅)alkyl-phenyl; phenyl;fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl;dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examplesof substituted (C₆-C₄₀)aryl are substituted (C₁-C₂₀)aryl; substituted(C₆-C₁₈)aryl; 2,4-bis[(C₂₀)alkyl]-phenyl; polyfluorophenyl;pentafluorophenyl; and fluoren-9-one-1-yl.

“(C₃-C₄₀)cycloalkyl” as used herein means a saturated cyclic hydrocarbonradical of from 3 to 40 carbon atoms that is unsubstituted orsubstituted by one or more R^(S). Other cycloalkyl groups (e.g.,(C_(x)-C_(y))cycloalkyl) are defined in an analogous manner as havingfrom x to y carbon atoms and being either unsubstituted or substitutedwith one or more R^(S). Examples of unsubstituted (C₃-C₄₀)cycloalkyl areunsubstituted (C₃-C₂₀)cycloalkyl, unsubstituted (C₃-C₁₀)cycloalkyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted(C₃-C₄₀)cycloalkyl are substituted (C₃-C₂₀)cycloalkyl, substituted(C₃-C₁₀)cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

Examples of (C₁-C₄₀)hydrocarbylene include unsubstituted or substituted(C₆-C₄₀)arylene, (C₃-C₄₀)cycloalkylene, and (C₁-C₄₀)alkylene (e.g.,(C₁-C₂₀)alkylene). In some embodiments, the diradicals are on the samecarbon atom (e.g., —CH₂—) or on adjacent carbon atoms (i.e.,1,2-diradicals), or are spaced apart by one, two, or more than twointervening carbon atoms (e.g., respective 1,3-diradicals,1,4-diradicals, etc.). Some diradicals include α,ω-diradical. Theα,ω-diradical is a diradical that has maximum carbon backbone spacingbetween the radical carbons. Some examples of (C₂-C₂₀)alkyleneα,ω-diradicals include ethan-1,2-diyl (i.e., —CH₂CH₂), propan-1,3-diyl(i.e., —CH₂CH₂CH₂—), 2-methylpropan-1,3-diyl (i.e., —CH₂CH(CH₃)CH₂—).Some examples of (C₆-C₄₀)arylene α,ω-diradicals include phenyl-1,4-diyl,napthalen-2,6-diyl, or napthalen-3,7-diyl.

“(C₁-C₄₀)alkylene” as used herein means a saturated straight chain orbranched chain diradical (i.e., the radicals are not on ring atoms) offrom 1 to 40 carbon atoms that is unsubstituted or substituted by one ormore R^(S). Examples of unsubstituted (C₁-C₄₀)alkylene are unsubstituted(C₁-C₂₀)alkylene, including unsubstituted-CH₂CH₂—, —(CH₂)₃—, —(CH₂)₄—,—(CH₂)₅—, —(CH₂)₆—, —(CH₂)₇—, —(CH₂)₈—, —CH₂C*HCH₃, and—(CH₂)₄C*(H)(CH₃), in which “C*” denotes a carbon atom from which ahydrogen atom is removed to form a secondary or tertiary alkyl radical.Examples of substituted (C₁-C₄₀)alkylene are substituted(C₁-C₂₀)alkylene, —CF₂—, —C(O)—, and —(CH₂)₁₄C(CH₃)₂(CH₂)₅— (i.e., a6,6-dimethyl substituted normal-1,20-eicosylene). Since as mentionedpreviously two R^(S) may be taken together to form a (C₁-C₁₈)alkylene,examples of substituted (C₁-C₄₀)alkylene also include1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane,2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and2,3-bis(methylene)bicyclo [2.2.2] octene.

“(C₃-C₄₀)cycloalkylene” as used herein means a cyclic diradical (i.e.,the radicals are on ring atoms) of from 3 to 40 carbon atoms that isunsubstituted or substituted by one or more R^(S).

“Heteroatom” as used herein refers to an atom other than hydrogen orcarbon. Examples of groups containing one or more than one heteroatominclude O, S, S(O), S(O)₂, Si(R^(C))₂, P(R^(P)), N(R^(N)), —N═C(R^(C))₂,—Ge(R^(C))₂—, or —Si(R^(C))—, where each R^(C) and each R^(P) isunsubstituted (C₁-C₁₈)hydrocarbyl or —H, and where each R^(N) isunsubstituted (C₁-C₁₈)hydrocarbyl. The term “heterohydrocarbon” refersto a molecule or molecular framework in which one or more carbon atomsare replaced with a heteroatom. The term “(C₁-C₄₀)heterohydrocarbyl”means a heterohydrocarbon radical of from 1 to 40 carbon atoms, and theterm “(C₁-C₄₀)heterohydrocarbylene” means a heterohydrocarbon diradicalof from 1 to 40 carbon atoms, and each heterohydrocarbon has one or moreheteroatoms. The radical of the heterohydrocarbyl is on a carbon atom ora heteroatom, and diradicals of the heterohydrocarbyl may be on: (1) oneor two carbon atom, (2) one or two heteroatoms, or (3) a carbon atom anda heteroatom. Each (C₁-C₄₀)heterohydrocarbyl and(C₁-C₄₀)heterohydrocarbylene may be unsubstituted or substituted (by oneor more R^(S)), aromatic or non-aromatic, saturated or unsaturated,straight chain or branched chain, cyclic (including mono- andpoly-cyclic, fused and non-fused polycyclic), or acyclic.

The (C₁-C₄₀)heterohydrocarbyl may be unsubstituted or substituted.Non-limiting examples of the (C₁-C₄₀)heterohydrocarbyl include(C₁-C₄₀)heteroalkyl, (C₁-C₄₀)hydrocarbyl-O—, (C₁-C₄₀)hydrocarbyl-S—,(C₁-C₄₀)hydrocarbyl-S(O)—, (C₁-C₄₀)hydrocarbyl-S(O)₂—,(C₁-C₄₀)hydrocarbyl-Si(R^(C))₂—, (C₁-C₄₀)hydrocarbyl-N(R^(N))—,C₄₀)hydrocarbyl-P(R^(P))—, (C₂-C₄₀)heterocyclo alkyl,(C₂-C₁₉)heterocycloalkyl-(C₁-C₂₀)alkylene,(C₃-C₂₀)cycloalkyl-(C₁-C₁₉)heteroalkylene, (C₂-C₁₉)heterocycloalkyl-(C₁-C₂₀)heteroalkylene, (C₁-C₅₀)heteroaryl,(C₁-C₁₉)heteroaryl-(C₁-C₂₀)alkylene,(C₆-C₂₀)aryl-(C₁-C₁₉)heteroalkylene, or(C₁-C₁₉)heteroaryl-(C₁-C₂₀)heteroalkylene.

“(C₁-C₄₀)heteroaryl” as used herein means an unsubstituted orsubstituted (by one or more R^(S)) mono-, bi- or tricyclicheteroaromatic hydrocarbon radical of from 1 to 40 total carbon atomsand from 1 to 10 heteroatoms, and the mono-, bi- or tricyclic radicalcomprises 1, 2 or 3 rings, respectively, wherein the 2 or 3 ringsindependently are fused or non-fused and at least one of the 2 or 3rings is heteroaromatic. Other heteroaryl groups (e.g.,(C_(x)-C_(y))heteroaryl generally, such as (C₁-C₁₂)heteroaryl) aredefined in an analogous manner as having from x to y carbon atoms (suchas 1 to 12 carbon atoms) and being unsubstituted or substituted by oneor more than one R^(S). The monocyclic heteroaromatic hydrocarbonradical is a 5-membered or 6-membered ring. The 5-membered ring has 5minus h carbon atoms, wherein h is the number of heteroatoms and may be1, 2, or 3; and each heteroatom may be O, S, N, or P. Examples of5-membered ring heteroaromatic hydrocarbon radical are pyrrol-1-yl;pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl;isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl;1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl;tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has6 minus h carbon atoms, wherein h is the number of heteroatoms and maybe 1 or 2 and the heteroatoms may be N or P. Examples of 6-membered ringheteroaromatic hydrocarbon radical are pyridine-2-yl; pyrimidin-2-yl;and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can bea fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring systembicyclic heteroaromatic hydrocarbon radical are indol-1-yl; andbenzimidazole-1-yl. Examples of the fused 6,6-ring system bicyclicheteroaromatic hydrocarbon radical are quinolin-2-yl; andisoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical canbe a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring system. An example ofthe fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. Anexample of the fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. Anexample of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An exampleof the fused 6,6,6-ring system is acrydin-9-yl.

The aforementioned heteroalkyl may be saturated straight or branchedchain radicals containing (C₁-C₄₀) carbon atoms, or fewer carbon atomsand one or more of the heteroatoms. Likewise, the heteroalkylene may besaturated straight or branched chain diradicals containing from 1 to 50carbon atoms and one or more than one heteroatoms. The heteroatoms, asdefined above, may include Si(R^(C))₃, Ge(R^(C))₃, Si(R^(C))₂,Ge(R^(C))₂, P(R^(P))₂, P(R^(P)), N(R^(N))₂, N(R^(N)), N, O, OR^(C), S,SR^(C), S(O), and S(O)₂, wherein each of the heteroalkyl andheteroalkylene groups are unsubstituted or substituted by one or moreR^(S).

Examples of unsubstituted (C₂-C₄₀)heterocycloalkyl are unsubstituted(C₂-C₂₀)heterocycloalkyl, unsubstituted (C₂-C₁₀)heterocycloalkyl,aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl,tetrahydrothiophen-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl,hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and2-aza-cyclodecyl.

“Halogen atom” or “halogen” as used herein mean the radical of afluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom(I). The term “halide” means anionic form of the halogen atom: fluoride(F⁻), chloride (Cl⁻), bromide (Br⁻), or iodide (I⁻).

“Saturated” as used herein means lacking carbon-carbon double bonds,carbon-carbon triple bonds, and (in heteroatom-containing groups)carbon-nitrogen, carbon-phosphorous, and carbon-silicon double bonds.Where a saturated chemical group is substituted by one or moresubstituents R^(S), one or more double and/or triple bonds optionallymay or may not be present in substituents R^(S). The term “unsaturated”means containing one or more carbon-carbon double bonds, carbon-carbontriple bonds, and (in heteroatom-containing groups) carbon-nitrogen,carbon-phosphorous, and carbon-silicon double bonds, not including anysuch double bonds that may be present in substituents R^(S), if any, orin (hetero) aromatic rings, if any.

As noted above, the first catalyst may, in embodiments, comprise aprocatalyst—such as, for example, the bis(biphenylphenoxy) procatalystdescribed above—and one or more cocatalysts that activate theprocatalyst. Suitable activating cocatalysts for use according toembodiments include alkyl aluminums; polymeric or oligomeric alumoxanes(also known as aluminoxanes); neutral or strong Lewis acids; andnon-polymeric, non-coordinating, ion-forming compounds (including theuse of such compounds under oxidizing conditions). Exemplary suitablecocatalysts include, but are not limited to: modified methyl aluminoxane(MMAO), bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyeborate(1⁻) amine, triethylaluminum (TEA), andcombinations thereof. A suitable activating technique is bulkelectrolysis. Combinations of one or more of the foregoing activatingcocatalysts and techniques are also contemplated. The term “alkylaluminum” as used herein means a monoalkyl aluminum dihydride ormonoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkylaluminum halide, or a trialkylaluminum. Examples of polymeric oroligomeric alumoxanes include methylalumoxane,triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

Lewis acid activators (cocatalysts) according to embodiments includeGroup 13 metal compounds containing from 1 to 3 (C₁-C₂₀)hydrocarbylsubstituents as described herein. In embodiments, Group 13 metalcompounds are tri((C₁-C₂₀)hydrocarbyl)-substituted-aluminum ortri((C₁-C₂₀)hydrocarbyl)-boron compounds. In other embodiments, Group 13metal compounds are tri(hydrocarbyl)-substituted-aluminum,tri(hydrocarbyl)-boron compounds, tri((C₁-C₁₀)alkyealuminum,tri((C₆-C₁₈)aryl)boron compounds, and halogenated (includingperhalogenated) derivatives thereof. In further embodiments, Group 13metal compounds are tris(fluoro-substituted phenyl)boranes,tris(pentafluorophenyl)borane. In some embodiments, the activatingcocatalyst is a tetrakis((C₁-C₂₀)hydrocarbyl borate (e.g. trityltetrafluoroborate) or a tri((C₁-C₂₀)hydrocarbyl)ammoniumtetra((C₁-C₂₀)hydrocarbyl)borane (e.g. bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl)borane). As used herein, the term “ammonium”means a nitrogen cation that is a ((C₁-C₂₀)hydrocarbyl)₄N⁺ a((C₁-C₂₀)hydrocarbyl)₃N(H)⁺, a ((C₁-C₂₀)hydrocarbyl)₂N(H)₂ ⁺,(C₁-C₂₀)hydrocarbylN(H)₃ ⁺, or N(H)₄ ⁺, wherein each(C₁-C₂₀)hydrocarbyl, when two or more are present, may be the same ordifferent.

Combinations of neutral Lewis acid activators (cocatalysts) as describedherein include mixtures comprising a combination of atri((C₁-C₄)alkyealuminum and a halogenated tri((C₆-C₁₈)aryl)boroncompound, especially a tris(pentafluorophenyl)borane. Other embodimentsare combinations of such neutral Lewis acid mixtures with a polymeric oroligomeric alumoxane, and combinations of a single neutral Lewis acid,especially tris(pentafluorophenyl)borane with a polymeric or oligomericalumoxane. Ratios of numbers of moles of (metal-ligand complex):(tris(pentafluoro-phenylborane):(alumoxane) [e.g., (Group 4 metal-ligandcomplex):(tris(pentafluoro-phenylborane):(alumoxane)] are from 1:1:1 to1:10:30, in other embodiments, from 1:1:1.5 to 1:5:10.

In embodiments, a ratio of total number of moles of one or moremetal-ligand complexes of Formula (I) to total number of moles of one ormore of the activating cocatalysts is from 1:10,000 to 100:1. In someembodiments, the ratio is at least 1:5000, in some other embodiments, atleast 1:1000; and 10:1 or less, and in some other embodiments, 1:1 orless. When an alumoxane alone is used as the activating cocatalyst, insome embodiments the number of moles of the alumoxane that are employedis at least 100 times the number of moles of the metal-ligand complex ofFormula (I). When tris(pentafluorophenyl)borane alone is used as theactivating cocatalyst, in some other embodiments, the number of moles ofthe tris(pentafluorophenyl)borane that are employed to the total numberof moles of one or more metal-ligand complexes of Formula (I) from 0.5:1to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activatingcocatalysts are generally employed in approximately mole quantitiesequal to the total mole quantities of one or more metal-ligand complexesof Formula (I).

The reaction conditions in the first reactor 110 for reacting ethylenemonomer, C₃-C₁₂ α-olefin comonomer, and, optionally, hydrogen in thepresence of the first catalyst—embodiments of which are providedabove—will now be described.

To facilitate the reaction of ethylene monomer with C₃-C₁₂ α-olefincomonomer in the presence of the first catalyst, in embodiments thefirst reactor 110 is heated to a temperature from 155° C. to 190° C.,such as from 160° C. to 190° C., from 165° C. to 190° C., from 170° C.to 190° C., from 175° C. to 190° C., from 180° C. to 190° C., or from185° C. to 190° C. In embodiments, the first reactor is heated to atemperature from 155° C. to 185° C., such as from 155° C. to 180° C.,from 155° C. to 175° C., from 155° C. to 170° C., from 155° C. to 165°C., or from 155° C. to 160° C. It should be understood that the abovetemperature ranges include the endpoints recited therein (e.g., “from155° C. to 190° C.” includes both 155° C. and 190° C.) and thetemperature of the first reactor 110 may be measured with anyconventional reactor temperature monitoring systems and software.

The feed stream 101 that is introduced in to the first reactor 110, inembodiments, comprises a high concentration of ethylene monomer. In someembodiments, the feed stream 101 comprises from 70 grams per liter (g/L)to 135 g/L ethylene monomer. In some embodiments, the feed stream 101comprises from 75 g/L to 135 g/L ethylene monomer, such as from 80 g/Lto 135 g/L ethylene monomer, from 85 g/L to 135 g/L ethylene monomer,from 90 g/L to 135 g/L ethylene monomer, from 95 g/L to 135 g/L ethylenemonomer, from 100 g/L to 135 g/L ethylene monomer, from 105 g/L to 135g/L ethylene monomer, from 110 g/L to 135 g/L ethylene monomer, from 115g/L to 135 g/L ethylene monomer, from 120 g/L to 135 g/L ethylenemonomer, from 125 g/L to 135 g/L ethylene monomer, or from 130 g/L to135 g/L ethylene monomer. In other embodiments, the feed stream 101comprises from 70 g/L to 130 g/L ethylene monomer, such as from 70 g/Lto 125 g/L ethylene monomer, from 70 g/L to 120 g/L ethylene monomer,from 70 g/L to 115 g/L ethylene monomer, from 70 g/L to 110 g/L ethylenemonomer, from 70 g/L to 105 g/L ethylene monomer, from 70 g/L to 100 g/Lethylene monomer, from 70 g/L to 95 g/L ethylene monomer, from 70 g/L to90 g/L ethylene monomer, from 70 g/L to 85 g/L ethylene monomer, from 70g/L to 80 g/L ethylene monomer, or from 70 g/L to 75 g/L ethylenemonomer.

The concentration of comonomer in the feed stream 101 is not limited andcan be present in a concentration from 0.0 g/L to 95.0 g/L, such as from5.0 g/L to 95.0 g/L, from 15.0 g/L to 95.0 g/L, from 25.0 g/L to 95.0g/L, from 35.0 g/L to 95.0 g/L, from 45.0 g/L to 95.0 g/L, from 55.0 g/Lto 95.0 g/L, from 65.0 g/L to 95.0 g/L, from 75.0 g/L to 95.0 g/L, orfrom 85.0 g/L to 95.0 g/L. In some embodiments, the concentration ofcomonomer in the feed stream 101 is from 0.0 g/L to 90.0 g/L, from 0.0g/L to 80.0 g/L, from 0.0 g/L to 70.0 g/L, from 0.0 g/L to 60.0 g/L,from 0.0 g/L to 50.0 g/L, from 0.0 g/L to 40.0 g/L, from 0.0 g/L to 30.0g/L, from 0.0 g/L to 20.0 g/L, or from 0.0 g/L to 10.0 g/L.

In embodiments, the first catalyst is present in the first reactor 110at a concentration from 0.06 micromole per liter (μmol/L) to 3.00 μmon,such as from 0.500 μmon to 3.00 μmon, from 1.00 μmon to 3.00 μmon, from1.50 μmon to 3.00 μmon, from 2.00 μmon to 3.00 μmon, or from 2.50 μmonto 3.00 μmon. In embodiments, the first catalyst is present in the firstreactor 110 at a concentration from 0.06 μmon to 2.50 μmon, such as from0.06 μmon to 2.00 μmon, from 0.06 μmon to 1.50 μmon, from 0.06 μmon to1.00 μmon, from 0.06 μmon to 0.500 μmon, from 0.06 μmon to 0.250 μmon,or from 0.06 μmon to 0.100 μmon.

Under these reaction conditions, ethylene monomer, C₃-C₁₂ α-olefincomonomer, and, optionally, hydrogen react in the presence of the firstcatalyst, such as, for example, the catalysts described above, to formthe first polymer fraction. In embodiments, this first polymer fractionis lower in density and lower in melt index (I₂) than the second polymerfraction formed in the mixer 130.

As described previously in this disclosure, at least the first polymerfraction, unreacted ethylene monomer, and unreacted C₃-C₁₂ α-olefincomonomer exit the first reactor 110 in effluent 111 a. A secondcatalyst is introduced to the effluent 111 a via second catalyst stream112 causing the unreacted ethylene monomer and unreacted C₃-C₁₂ α-olefincomonomer to react in the presence of the second catalyst and form asecond polymer fraction. The high concentration of ethylene monomerpresent in both the feed stream 101 and the effluent 111 a ensures thereis sufficient ethylene present when the second catalyst stream 112 isintroduced to the effluent 111 a at mixer 130 to allow for formation ofthe second polymer fraction.

In embodiments, the effluent 111 a comprises from 20 grams per liter(g/L) to 45 g/L ethylene monomer. In some embodiments, the effluent 111a comprises from 25 g/L to 45 g/L ethylene monomer, such as from 30 g/Lto 45 g/L ethylene monomer, from 35 g/L to 45 g/L ethylene monomer, orfrom 40 g/L to 45 g/L ethylene monomer. In other embodiments, effluent111 a comprises from 20 g/L to 40 g/L ethylene monomer, such as from 20g/L to 35 g/L ethylene monomer, from 20 g/L to 30 g/L ethylene monomer,or from 20 g/L to 25 g/L ethylene monomer.

As the modified effluent 111 b—comprising ethylene monomer, C₃-C₁₂α-olefin comonomer, second catalyst, and second polymer fraction—travelsthrough the mixer 130 toward the second reactor 120, the ethylenemonomer and C₃-C₁₂ α-olefin comonomer present in the modified effluent111 b continue to react in the presence of the second catalyst to formsecond polymer fraction. It should be understood that the temperaturewhere the second catalyst stream 112 is introduced to the effluent 111 ais approximately equal to the temperature within the first reactor 110(i.e., from 155° C. to 190° C.), which is lower than the temperature inthe second reactor. Further, although ethylene monomer is reacted in thefirst reactor 110 to form the first polymer fraction, the amount ofethylene introduced into the first reactor 110 is such that theconcentration of unreacted ethylene monomer in the effluent 111 a issufficient to form second polymer fraction. In some embodiments,additional, fresh ethylene monomer may be added to either the effluent111 a (i.e., before the second catalyst stream 112 is introduced to theeffluent) or to the modified effluent 111 b (i.e., after the secondcatalyst stream 112 is introduced to the effluent). In embodiments,reactions of ethylene monomer and C₃-C₁₂ α-olefin comonomer in thepresence of the second catalyst occur in the mixer 130. Reactingethylene monomer and C₃-C₁₂ α-olefin comonomer in the presence of thesecond catalyst before the modified effluent 111 b is introduced intothe second reactor 120 produces a second polymer fraction that has ahigh density fraction, which in turn results in a ethylene-based polymerwith better balance of density and melt index. Without being bound byany particular theory, it is believed that the relatively lowtemperature of the modified effluent 111 b and the high concentration ofethylene monomer in the modified effluent 111 b results in increasedpropagation rates, such as, for example, propagation rates 2 to 4 timeshigher than propagation rates achieved in conventional processes where asecond catalyst is added at the second reactor and at highertemperatures. It is believed that the increased propagation rateprovides a high density fraction in the ethylene-based polymer.

The second catalyst that is introduced to the effluent 111 a via thesecond catalyst stream 112 is, in embodiments, a Ziegler-Natta catalystor a second molecular catalyst—which were described in detail above. Inembodiments, exemplary Ziegler-Natta catalysts are those derived from(1) organomagnesium compounds, (2) alkyl halides or aluminum halides orhydrogen chloride, and (3) a transition metal compound. Examples of suchcatalysts are described in U.S. Pat. No. 4,314,912 (Lowery, Jr. et al.),U.S. Pat. No. 4,547,475 (Glass et al.), and U.S. Pat. No. 4,612,300(Coleman, III), the teachings of which are incorporated herein byreference in their entirety. The Ziegler-Natta procatalyst may be formedby (a) reacting a hydrocarbon-soluble organomagnesium compound orcomplex thereof and an active non-metallic or metallic halide to form ahalogenated magnesium support; b) contacting the magnesium halidesupport with a conditioning compound containing an element selected fromthe group consisting of boron, aluminum, gallium, indium and telluriumunder conditions sufficient to form a conditioned magnesium halidesupport; (c) contacting the magnesium halide support and a compoundcontaining, as a first metal, titanium, to form a supported titaniumcompound; and (d) optionally, contacting the supported titanium compoundand a second metal and optionally a third metal independently selectedfrom the transition metal series, provided that the second metal and thethird metal are not the same; and further provided that the molar ratioof the magnesium to a combination of the titanium and the second andthird metals ranges from 30:1 to 5:1; all under conditions sufficient toform a procatalyst.

Particularly suitable organomagnesium compounds for use in Ziegler-Nattacatalysts include, for example, hydrocarbon solubledihydrocarbylmagnesium such as the magnesium dialkyls and the magnesiumdiaryls. Exemplary suitable magnesium dialkyls include particularlyn-butyl-secbutylmagnesium, diisopropylmagnesium, di-n-hexylmagnesium,isopropyl-n-butyl-magnesium, ethyl-n-hexylmagnesium,ethyl-n-butylmagnesium, di-n-octylmagnesium and others wherein the alkylhas from 1 to 20 carbon atoms. Exemplary suitable magnesium diarylsinclude diphenylmagnesium, dibenzylmagnesium and ditolylmagnesium.Suitable organomagnesium compounds include alkyl and aryl magnesiumalkoxides and aryloxides and aryl and alkyl magnesium halides. In someembodiments, the organomagnesium compound is a halogen-freeorganomagnesium.

The modified effluent 111 b—which comprises unreacted methylene,unreacted C₃-C₁₂ α-olefin comonomer, second catalyst, first polymerfraction, and second polymer fraction—is present in the mixer 130 for aduration from 3 minutes to 6 minutes, such as from 3 minutes to 5minutes, or from 3 minutes to 4 minutes before it is introduced into thesecond reactor 120.

After the modified effluent 111 b is introduced into the second reactor120, which is a non-agitated solution polymerization reactor, themodified effluent 111 b is heated to a temperature that is greater thanthe temperature in the first reactor 110 and greater than thetemperature of the modified effluent 111 b in the mixer 130. Inembodiments, the temperature within the second reactor 120 is from 190°C. to 265° C. The temperature within the second reactor 120 is, in someembodiments, from 195° C. to 265° C., such as from 200° C. to 265° C.,from 205° C. to 265° C., from 210° C. to 265° C., from 215° C. to 265°C., from 220° C. to 265° C., from 225° C. to 265° C., from 230° C. to265° C., from 235° C. to 265° C., from 240° C. to 265° C., from 240° C.to 265° C., from 245° C. to 265° C., from 250° C. to 265° C., or from255° C. to 265° C. In other embodiments, the temperature within thesecond reactor is from 190° C. to 260° C., such as from 190° C. to 255°C., from 190° C. to 250° C., from 190° C. to 245° C., from 190° C. to240° C., from 190° C. to 235° C., from 190° C. to 230° C., from 190° C.to 225° C., from 190° C. to 220° C., from 190° C. to 215° C., from 190°C. to 210° C., from 190° C. to 205° C., from 190° C. to 200° C., or from190° C. to 195° C. It should be understood that the above temperatureranges include the endpoints recited therein (e.g., “from 190° C. to265° C.” includes both 190° C. and 265° C.) and the temperature of thesecond reactor 120 may be measured with any conventional reactortemperature monitoring systems and software.

The unreacted ethylene monomer and unreacted C₃-C₁₂ α-olefin comonomerin the modified effluent 111 b that enters the second reactor 120 willreact in the presence of the second catalyst to form additional secondpolymer fraction. In addition, a second feed stream 121 that comprisesethylene monomer and C₃-C₁₂ α-olefin comonomer in solvent is introducedinto the second reactor 120. The ethylene monomer and C₃-C₁₂ α-olefincomonomer from the second feed stream 121 will also react in thepresence of the second catalyst to form additional second polymerfraction. It should be understood that although FIG. 1 depicts secondfeed stream 121 as a single feed stream, the components may beindividually introduced into the second reactor 120.

After a sufficient amount of time in the second reactor 120, productstream 122 that comprises an ethylene-based polymer exits the secondreactor 120. Properties of the ethylene-based polymer present in productstream 122 will be described in more detail below. Although not shown inFIG. 1, it should be understood that any unreacted ethylene monomer,unreacted C₃-C₁₂ α-olefin comonomer, and solvent present in productstream 122 may be separated from the ethylene-based polymer and recycledback to the system 100 or 200 in feed stream 101 to the first reactor110 or in second feed stream 121 to the second reactor 120.

The over conversion rate of ethylene monomer in the system 100 is from90% to 94%, such as from 91% to 94%, from 92% to 94%, or from 93% to94%.

Ethylene-Based Polymer Properties

Exemplary properties of ethylene-based polymers produced according toembodiments disclosed and described herein will now be provided. Asnoted above, and without being bound to any particular theory, it isbelieved that the combination of the exemplary properties listed belowis made possible by the processes and systems disclosed and describedhereinabove.

According to embodiments, the ethylene-based polymer may have a densityfrom 0.900 to 0.925 g/cc measured according to ASTM D792. In someembodiments, the ethylene-based polymer has a density from 0.910 g/cc to0.925 g/cc, such as from 0.915 g/cc to 0.925 g/cc, or from 0.920 g/cc to0.925 g/cc. In other embodiments the ethylene-based polymer has adensity from 0.910 g/cc to 0.920 g/cc, such as from 0.910 g/cc to 0.915g/cc. In yet other embodiments, the ethylene-based polymer has a densityfrom 0.912 g/cc to 0.920 g/cc, or from 0.910 g/cc to 0.918 g/cc. Itshould be understood that the above density ranges include the endpointsrecited therein.

The ethylene-based polymers of embodiments have a high density fraction(HDF)—measured by crystallization elution fractionation (CEF)integration at temperatures from 93° C. to 119° C.—from 3.0% to 10.0%,such as from 3.5% to 10.0%, from 4.0% to 10.0%, from 5.5% to 10.0%, from6.0% to 10.0%, from 6.5% to 10.0%, from 7.0% to 10.0%, from 7.5% to10.0%, from 8.0% to 10.0%, from 8.5% to 10.0%, from 9.0% to 10.0%, orfrom 9.5% to 10.0. In other embodiments, the ethylene-based polymers ofembodiments have an HDF from 3.0% to 9.5%, such as from 3.0% to 9.0%,from 3.0% to 8.5%, from 3.0% to 8.0%, from 3.0% to 7.5%, from 3.0% to7.0%, from 3.0% to 6.5%, from 3.0% to 6.0%, from 3.0% to 5.5%, from 3.0%to 5.0%, from 3.0% to 4.5%, or from 3.0% to 4.0%. In still otherembodiments the ethylene-based polymers of embodiments have an HDF from3.5% to 9.5%, such as from 4.0% to 9.0%, from 4.5% to 8.5%, from 5.0% to8.0%, from 5.5% to 7.5%, or from 6.0% to 7.0. It should be understoodthat the above HDF ranges include the endpoints recited therein.

In embodiments, the ethylene-based polymer has a melt index(I₂)—measured according to ASTM D 1238 at a load of 2.16 kg—from 1.0grams per 10 minutes (g/10 mins) to 6.0 g/10 mins, such as from 1.5 g/10mins to 6.0 g/10 mins, from 2.0 g/10 mins to 6.0 g/10 mins, from 2.5g/10 mins to 6.0 g/10 mins, from 3.0 g/10 mins to 6.0 g/10 mins, from3.5 g/10 mins to 6.0 g/10 mins, from 4.0 g/10 mins to 6.0 g/10 mins,from 4.5 g/10 mins to 6.0 g/10 mins, from 5.0 g/10 mins to 6.0 g/10mins, or from 5.5 g/10 mins to 6.0 g/10 mins. In other embodiments, theethylene-based polymer has an 12 from 1.0 g/10 mins to 5.5 g/10 mins,such as 1.0 g/10 mins to 5.5 g/10 mins, from 1.0 g/10 mins to 4.5 g/10mins, from 1.0 g/10 mins to 4.0 g/10 mins, from 1.0 g/10 mins to 3.5g/10 mins, from 1.0 g/10 mins to 3.0 g/10 mins, from 1.0 g/10 mins to2.5 g/10 mins, from 1.0 g/10 mins to 2.0 g/10 mins, or from 1.0 g/10mins to 1.5 g/10 mins. In yet other embodiments, the ethylene-basedpolymer has an 12 from 1.0 g/10 mins to 4.5 g/10 mins, such as from 1.5g/10 mins to 4.0 g/10 mins, from 2.0 g/10 mins to 4.0 g/10 mins, from3.0 g/10 mins to 4.0 g/10 mins, or from 3.0 g/10 mins to 3.5 g/10 mins.It should be understood that the above 12 ranges include the endpointsrecited therein.

The ethylene-based polymer may have an I₁₀/I₂ ratio—where I₂ is the meltindex when measured according to ASTM D 1238 at a load of 2.16 kg andtemperature of 190° C. and I₁₀ is the melt index when measured accordingto ASTM D 1238 at a load of 10 kg and temperature of 190° C.—from 5.5 to6.9, such as from 5.7 to 6.9, from 5.9 to 6.9, from 6.0 to 6.9, from 6.2to 6.9, from 6.4 to 6.9, from 6.6 to 6.9, or from 6.8 to 6.9. In otherembodiments, ethylene-based polymer may have an I₁₀/I₂ ratio from 5.5 to6.8, such as from 5.5 to 6.6, from 5.5 to 6.4, from 5.5 to 6.2, from 5.5to 6.0, from 5.5 to 5.8, or from 5.5 to 5.6. In still other embodiments,the ethylene-based polymer may have an I₁₀/I₂ ratio from 5.6 to 6.8,such as from 5.7 to 6.7, from 5.8 to 6.6, from 5.9 to 6.5, from 6.0 to6.4, or from 6.1 to 6.3. In still other embodiments, the ethylene-basedpolymer may have an I₁₀/I₂ ratio from 5.5 to 6.5. It should beunderstood that the above I₁₀/I₂ ratio ranges include the endpointsrecited therein.

The short chain branching distribution (SCBD) of ethylene-based polymersis, according to embodiments, less than 10° C.—measured by CEF fullwidth at half height. In some embodiments, the SCBD of ethylene-basedpolymers is less than 8.0° C., such as less than 7.5° C., less than 7.0°C., less than 6.5° C., less than 6.0° C., less than 5.0° C. It should beunderstood that the above SCBD ranges include the endpoints recitedtherein.

The ethylene-based polymer has, according to embodiments, a zero shearviscosity ratio (ZSVR) from 1.1 to 3.0, such as from 1.2 to 3.0, from1.3 to 3.0, from 1.4 to 3.0, from 1.5 to 3.0, from 1.6 to 3.0, from 1.7to 3.0, from 1.8 to 3.0, from 1.9 to 3.0, from 2.0 to 3.0, from 2.1 to3.0, from 2.2 to 3.0, from 2.3 to 3.0, from 2.4 to 3.0, from 2.5 to 3.0,from 2.6 to 3.0, from 2.7 to 3.0, from 2.8 to 3.0, or from 2.9 to 3.0.In some embodiments, the ethylene-based polymer has a zero shearviscosity ration from 1.1 to 2.9, from 1.1 to 2.8, from 1.1 to 2.7, from1.1 to 2.6, from 1.1 to 2.5, from 1.1 to 2.4, such as from 1.1 to 2.3,from 1.1 to 2.2, from 1.1 to 2.2, from 1.1 to 2.1, from 1.1 to 2.0, from1.1 to 1.9, from 1.1 to 1.8, from 1.1 to 1.7, from 1.1 to 1.6, from 1.1to 1.5, from 1.1 to 1.4, from 1.1 to 1.3, or from 1.1 to 1.2. In stillother embodiments, the ethylene-based polymer has a zero shear viscosityratio from 1.2 to 2.9, such as from 1.3 to 2.8, from 1.4 to 2.7, from1.5 to 2.6, from 1.6 to 2.5, from 1.7 to 2.4, from 1.8 to 2.3, from 1.9to 2.2, or from 2.0 to 2.1. It should be understood that the above zeroshear viscosity ratio ranges include the endpoints recited therein.

An ethylene-based polymer, according to embodiments, comprises from 70.0weight percent (wt. %) to 95.0 wt. % of the first polymer fraction andfrom 8.0 wt. % to 30.0 wt. % of the second polymer fraction. In someembodiments, the ethylene-based polymer comprises from 72.0 wt. % to95.0 wt. % of the first polymer fraction, such as from 74.0 wt. % to95.0 wt. % of the first polymer fraction, from 76.0 wt. % to 95.0 wt. %of the first polymer fraction, from 78.0 wt. % to 95.0 wt. % of thefirst polymer fraction, from 80.0 wt. % to 95.0 wt. % of the firstpolymer fraction, from 82.0 wt. % to 95.0 wt. % of the first polymerfraction, from 84.0 wt. % to 95.0 wt. % of the first polymer fraction,from 86.0 wt. % to 95.0 wt. % of the first polymer fraction, from 88.0wt. % to 95.0 wt. % of the first polymer fraction, or from 90.0 wt. % to95.0 wt. % of the first polymer fraction. In other embodiments, theethylene-based polymer comprises from 70.0 wt. % to 92.0 wt. % of thefirst polymer fraction, such as from 70.0 wt. % to 90.0 wt. % of thefirst polymer fraction, from 70.0 wt. % to 88.0 wt. % of the firstpolymer fraction, from 70.0 wt. % to 86.0 wt. % of the first polymerfraction, from 70.0 wt. % to 84.0 wt. % of the first polymer fraction,from 70.0 wt. % to 82.0 wt. % of the first polymer fraction, from 70.0wt. % to 80.0 wt. % of the first polymer fraction, from 70.0 wt. % to78.0 wt. % of the first polymer fraction, from 70.0 wt. % to 76.0 wt. %of the first polymer fraction, from 70.0 wt. % to 74.0 wt. % of thefirst polymer fraction, or from 70.0 wt. % to 72.0 wt. % of the firstpolymer fraction. In still other embodiments, the ethylene-based polymercomprises from 72.0 wt. % to 92.0 wt. % of the first polymer fraction,such as from 74.0 wt. % to 90.0 wt. % of the first polymer fraction,from 76.0 wt. % to 88.0 wt. % of the first polymer fraction, from 78.0wt. % to 86.0 wt. % of the first polymer fraction, or from 80.0 wt. % to84.0 wt. % of the first polymer fraction. It should be understood thatthe above weight percent ranges include the endpoints recited therein.

In some embodiments, the ethylene-based polymer comprises from 5.0 wt. %to 30.0 wt. % of the second polymer fraction, such as from 8.0 wt. % to30.0 wt. % of the second polymer fraction, from 10.0 wt. % to 30.0 wt. %of the second polymer fraction, from 12.0 wt. % to 30.0 wt. % of thesecond polymer fraction, from 14.0 wt. % to 30.0 wt. % of the secondpolymer fraction, from 16.0 wt. % to 30.0 wt. % of the second polymerfraction, from 18.0 wt. % to 30.0 wt. % of the second polymer fraction,from 20.0 wt. % to 30.0 wt. % of the second polymer fraction, from 22.0wt. % to 30.0 wt. % of the second polymer fraction, from 24.0 wt. % to30.0 wt. % of the second polymer fraction, from 26.0 wt. % to 30.0 wt. %of the second polymer fraction, or from 28.0 wt. % to 30.0 wt. % of thesecond polymer fraction. In other embodiments, the ethylene-basedpolymer comprises from 5.0 wt. % to 28.0 wt. % of the second polymerfraction, such as from 5.0 wt. % to 26.0 wt. % of the second polymerfraction, from 5.0 wt. % to 24.0 wt. % of the second polymer fraction,from 5.0 wt. % to 22.0 wt. % of the second polymer fraction, from 5.0wt. % to 20.0 wt. % of the second polymer fraction, from 5.0 wt. % to18.0 wt. % of the second polymer fraction, from 5.0 wt. % to 16.0 wt. %of the second polymer fraction, from 5.0 wt. % to 14.0 wt. % of thesecond polymer fraction, from 5.0 wt. % to 12.0 wt. % of the secondpolymer fraction, from 5.0 wt. % to 10.0 wt. % of the second polymerfraction, or from 5.0 wt. % to 8.0 wt. % of the second polymer fraction.In still other embodiments, the ethylene-based polymer comprises from5.0 wt. % to 28.0 wt. % of the second polymer fraction, from 6.0 wt. %to 26.0 wt. % of the second polymer fraction, from 8.0 wt. % to 24.0 wt.% of the second polymer fraction, from 10.0 wt. % to 22.0 wt. % of thesecond polymer fraction, from 12.0 wt. % to 20.0 wt. % of the secondpolymer fraction, or from 14.0 wt. % to 18.0 wt. % of the second polymerfraction. It should be understood that the above weight percent rangesinclude the endpoints recited therein.

The amount of each polymer fraction in the ethylene-based polymer may beadjusted based on the application or use. For example, a differentbalance of properties may be desirable in low temperature applications(e.g., below 0° C.) versus applications where the ethylene-based polymeris subjected to higher temperatures (e.g., temperatures greater than 40°C.).

In embodiments, the melt index and density of the second polymerfraction consists of the polymer fraction formed in the mixer 130 andthe reaction environment of the second reactor 120. The polymer fractionmade in the mixer 130 has a lower melt index (MI), and the polymerfraction formed in the second reactor 120 has higher MI (e.g., about 4times higher than polymer fraction formed in the mixer 130). Thecombined second polymer fraction formed in the mixer 130 and the secondreactor 120 has a high density fraction that is greater than the densityof the first ethylene-based polymer fraction by at least 0.03 g/cc, suchas greater than the density by at least 0.04 g/cc as shown by the CEFpeak temperatures. In addition, using processes for forming anethylene-based polymer according to embodiments disclosed and describedherein, the final ethylene-based polymer (i.e., including the firstpolymer fraction and the second polymer fraction) has a higher densityand higher melt index (I₂) than the first polymer fraction. Also, theportion of the second polymer fraction formed in the mixer has a highermolecular weight than the portion of the second polymer fraction formedin the second, non-agitated reactor.

In some processes, processing aids, such as plasticizers, can also beincluded in the ethylene-based polymer product. These aids include, butare not limited to, the phthalates, such as dioctyl phthalate anddiisobutyl phthalate, natural oils such as lanolin, and paraffin,naphthenic and aromatic oils obtained from petroleum refining, andliquid resins from rosin or petroleum feedstocks. Exemplary classes ofoils useful as processing aids include white mineral oil such as KAYDOLoil (Chemtura Corp.; Middlebury, Conn.) and SHELLFLEX 371 naphthenic oil(Shell Lubricants; Houston, Tex.). Another suitable oil is TUFFLO oil(Lyondell Lubricants; Houston, Tex.).

In some processes, ethylene-based polymer compositions are treated withone or more stabilizers, for example, antioxidants, such as IRGANOX 1010and IRGAFOS168 (Ciba Specialty Chemicals; Glattbrugg, Switzerland). Ingeneral, polymers are treated with one or more stabilizers before anextrusion or other melt processes. In other embodiment processes, otherpolymeric additives include, but are not limited to, ultraviolet lightabsorbers, antistatic agents, pigments, dyes, nucleating agents,fillers, slip agents, fire retardants, plasticizers, processing aids,lubricants, stabilizers, smoke inhibitors, viscosity control agents andanti-blocking agents. The ethylene-based polymer composition may, forexample, comprise less than 10 percent by the combined weight of one ormore additives, based on the weight of the ethylene-based polymercomposition.

In some embodiments, one or more antioxidants may further be added intothe ethylene-based polymer compositions and/or the compounded polymer.The ethylene-based polymer composition may contain any amount of one ormore antioxidants. For example, the ethylene-based polymer compositionsmay comprise from 200 to 600 parts of one or more phenolic antioxidantsper one million parts of the ethylene-based polymer compositions. Inaddition, the ethylene-based polymer composition may comprise from 800to 1200 parts of a phosphite-based antioxidant per one million parts ofethylene-based polymer compositions.

Additives and adjuvants may be added to the ethylene-based polymercompositions post-formation. Suitable additives include fillers, such asorganic or inorganic particles, including clays, talc, titanium dioxide,zeolites, powdered metals, organic or inorganic fibers, including carbonfibers, silicon nitride fibers, steel wire or mesh, and nylon orpolyester cording, nano-sized particles, clays, and so forth;tackifiers, oil extenders, including paraffinic or napthelenic oils; andother natural and synthetic polymers, including other polymers that areor can be made according to the embodiment methods.

Film Composition and Properties

In embodiments, polymer-based films may be formed with compositionscomprising ethylene-based polymers disclosed and described herein. Insome embodiments, films may be made from a composition comprising LLDPEaccording to embodiments disclosed and described herein (e.g., LLDPEhaving one or more of the HDF, I₁₀/I₂ ratio, SCBD, etc. disclosedherein), LDPE, and a pore former. In one or more embodiments,polymer-based films comprise from 20.0 weight percent (wt %) to 69.5 wt% LLDPE according to embodiments disclosed and described herein, from0.5 wt % to 10.0 wt % LDPE, and from 30.0 wt % to 70.0 wt % pore former.It should be understood that the above weight percent ranges include theendpoints recited therein.

In embodiments, films may comprise from 20.0 wt % to 69.5 wt % LLDPEaccording to embodiments disclosed and described herein, such as from25.0 wt % to 69.5 wt %, from 30.0 wt % to 69.5 wt %, from 35.0 wt % to69.5 wt %, from 40.0 wt % to 69.5 wt %, from 45.0 wt % to 69.5 wt %,from 50.0 wt % to 69.5 wt %, from 55.0 wt % to 69.5 wt %, from 60.0 wt %to 69.5 wt %, or from 65.0 wt % to 69.5 wt %. In other embodiments,films may comprise from 20.0 wt % to 65.0 wt % LLDPE according toembodiments disclosed and described herein, such as from 20.0 wt % to60.0 wt %, from 20.0 wt % to 55.0 wt %, from 20.0 wt % to 50.0 wt %,from 20.0 wt % to 45.0 wt %, from 20.0 wt % to 40.0 wt %, from 20.0 wt %to 35.0 wt %, from 20.0 wt % to 30.0 wt %, or from 20.0 wt % to 25.0 wt%. In still other embodiments, films may comprise from 25.0 wt % to 65.0wt % LLDPE according to embodiments disclosed and described herein, suchas from 30.0 wt % to 60.0 wt %, from 35.0 wt % to 55.0 wt %, or from40.0 wt % to 50.0 wt %. In further embodiments, films may comprise from40.0 wt % to 60.0 wt % LLDPE according to embodiments disclosed anddescribed herein. It should be understood that the above weight percentranges include the endpoints recited therein.

In embodiments, films may include 0.0 wt % LDPE. In some embodiments,films may comprise from 0.0 wt % to 10.0 wt %, such as from 0.5 wt % to10.0 wt % LDPE, from 1.0 wt % to 10.0 wt %, from 1.5 wt % to 10.0 wt %,from 2.0 wt % to 10.0 wt %, from 2.5 wt % to 10.0 wt %, from 3.0 wt % to10.0 wt %, from 3.5 wt % to 10.0 wt %, from 4.0 wt % to 10.0 wt %, from4.5 wt % to 10.0 wt %, from 5.0 wt % to 10.0 wt %, from 5.5 wt % to 10.0wt %, from 6.0 wt % to 10.0 wt %, from 6.5 wt % to 10.0 wt %, from 7.0wt % to 10.0 wt %, from 7.5 wt % to 10.0 wt %, from 8.0 wt % to 10.0 wt%, from 8.5 wt % to 10.0 wt %, from 9.0 wt % to 10.0 wt %, or from 9.5wt % to 10.0 wt %. In some embodiments, films may comprise from 0.5 wt %to 9.5 wt % LDPE, such as from 0.5 wt % to 9.0 wt %, from 0.5 wt % to8.5 wt %, from 0.5 wt % to 8.0 wt %, from 0.5 wt % to 7.5 wt %, from 0.5wt % to 7.0 wt %, from 0.5 wt % to 6.5 wt %, from 0.5 wt % to 6.0 wt %,from 0.5 wt % to 5.5 wt %, from 0.5 wt % to 5.0 wt %, from 0.5 wt % to4.5 wt %, from 0.5 wt % to 4.0 wt %, from 0.5 wt % to 3.5 wt %, from 0.5wt % to 3.0 wt %, from 0.5 wt % to 2.5 wt %, from 0.5 wt % to 2.0 wt %,from 0.5 wt % to 1.5 wt %, or from 0.5 wt % to 1.0 wt %. In still otherembodiments, films may comprise from 1.0 wt % to 9.5 wt % LDPE, such asfrom 1.5 wt % to 9.0 wt %, from 2.0 wt % to 8.5 wt %, from 2.5 wt % to8.0 wt %, from 3.0 wt % to 7.5 wt %, from 3.5 wt % to 7.0 wt %, from 4.0wt % to 6.5 wt %, from 4.5 wt % to 6.0 wt %, or from 5.0 wt % to 5.5 wt%. It should be understood that the above weight percent ranges includethe endpoints recited therein.

As described herein, the term “LDPE” is defined to mean that the polymeris partly or entirely homopolymerized or copolymerized in autoclave ortubular reactors at pressures above 14,500 psi (100 MPa) with the use offree-radical initiators, such as peroxides (see, for example, U.S. Pat.No. 4,599,392, which is hereby incorporated by reference). LDPE resinstypically have a density in the range of 0.916 to 0.940 g/cm. The LDPEused in films, according to some embodiments, may be AGILITY™ EC 7000,LDPE 450E, LDPE 410E, LDPE 310E, and LDPE PG7008 manufactured by The DowChemical Company.

Films according to embodiments include from 30.0 wt % to 70.0 wt % of apore former, such as from 35.0 wt % to 70.0 wt %, from 40.0 wt % to 70.0wt %, from 45.0 wt % to 70.0 wt %, from 50.0 wt % to 70.0 wt %, from55.0 wt % to 70.0 wt %, from 60.0 wt % to 70.0 wt %, or from 65.0 wt %to 70.0 wt %. In other embodiments, films include from 30.0 wt % to 65.0wt % pore former, such as from 30.0 wt % to 60.0 wt %, from 30.0 wt % to55.0 wt %, from 30.0 wt % to 50.0 wt %, from 30.0 wt % to 45.0 wt %,from 30.0 wt % to 40.0 wt %, or from 30.0 wt % to 35.0 wt %. In yetother embodiments, films include from 35.0 wt % to 65.0 wt % poreformer, such as from 40.0 wt % to 60.0 wt %, or from 45.0 wt % to 55.0wt %. It should be understood that the above weight percent rangesinclude the endpoints recited therein.

Pore formers that may be used in embodiments include calcium carbonate(CaCO₃), such as Filmlink™ 500 manufactured by Imerys or Omyafilm™ 753manufactured by Omya.

Films may be formed from the compositions disclosed herein by anyprocess, such as processes disclosed in U.S. Pat. Nos. 6,176,952;3,338,992; 3,502,538; 3,502,763; 3,849,241; 4,041,203; 4,340,563;4,374,888; 5,169,706; 7,230,511 and WO 2017/152065 all of which areincorporated herein by reference in their entirety.

The films formed herein are, according to embodiments, machine-directionoriented films. In various embodiments, the machine-direction orientedfilms may have an orientation ratio from 2.5× to 6.0×, such as from 3.0×to 6.0×, from 3.5× to 6.0×, from 4.0× to 6.0×, from 4.5× to 6.0×, from5.0× to 6.0×, or from 5.5× to 6.0×. In other embodiments, themachine-direction oriented films may have an orientation ratio from 2.5×to 5.5×, such as from 2.5× to 5.0×, from 2.5× to 4.5×, from 2.5× to4.0×, from 2.5× to 3.5×, or from 2.5× to 3.0×. In still otherembodiments, the machine-direction oriented films may have anorientation ratio from 3.0× to 5.5×, such as from 3.5× to 5.0×, or from4.0× to 4.5×. It should be understood that the above orientation ratioranges include the endpoints recited therein. The above stretch ratio iscalculated as ratio of the velocity of the film exiting the MDO unit tothe velocity of the film entering the MDO unit.

Properties of films made from the combinations of LLDPE, LDPE, and poreformers disclosed herein will now be described. It should be understoodthat various films will have one or more of the properties disclosedherein, and that various combinations of LLDPE, LDPE, and pore formersmay be combined to achieve a desired balance of properties depending onthe end use of the film. As disclosed hereinabove, by using acombination of LLDPE as disclosed and described herein, LDPE, and poreformers, a desirable balance of properties may be achieved. Accordingly,one or more of the properties of films made according to embodimentsdisclosed herein may be similar to the same property in commerciallyavailable films. However, where one property of films made according toembodiments disclosed herein is similar to that property in commerciallyavailable films, another property of the film made according toembodiments disclosed herein will be superior to the commerciallyavailable film. Thus, it is a combination of all properties of filmsmade according to embodiments disclosed herein that shows the improvedperformance of films made according to embodiments disclosed herein. Forinstance, a film made according to embodiments disclosed herein may havea similar hydrostatic pressure as a commercially available film, but thetear resistance in the film made according to embodiments disclosedherein may, in embodiments, be superior to the tear resistance of thecommercially available film.

According to embodiments, films may have an average machine directiontear—according to Elmendorf Tear ASTM D 1922 measured at 14 grams persquare meter (gsm)—that is greater than or equal to 5.0 grams force(g_(f)), such as greater than or equal to 5.1 g_(f), greater than orequal to 5.2 g_(f), greater than or equal to 5.3 g_(f), greater than orequal to 5.4 g_(f), greater than or equal to 5.5 g_(f), greater than orequal to 5.6 g_(f), greater than or equal to 5.7 g_(f), greater than orequal to 5.8 g_(f), greater than or equal to 5.9 g_(f), or greater thanor equal to 6.0 g_(f). In embodiments, films may have an average machinedirection tear from 5.0 g_(f) to 7.0 g_(f), such as from 5.2 g_(f) to7.0 g_(f), from 5.4 g_(f) to 7.0 g_(f), from 5.6 g_(f) to 7.0 g_(f),from 5.8 g_(f) to 7.0 g_(f), from 6.0 g_(f) to 7.0 g_(f), from 6.2 g_(f)to 7.0 g_(f), from 6.4 g_(f) to 7.0 g_(f), from 6.6 g_(f) to 7.0 g_(f),or from 6.8 g_(f) to 7.0 g_(f). In other embodiments, films may have anaverage machine direction tear from 5.0 g_(f) to 6.8 g_(f), such as from5.0 g_(f) to 6.6 g_(f), from 5.0 g_(f) to 6.4 g_(f), from 5.0 g_(f) to6.2 g_(f), from 5.0 g_(f) to 6.0 g_(f), from 5.0 g_(f) to 5.8 g_(f),from 5.0 g_(f) to 5.6 g_(f), from 5.0 g_(f) to 5.4 g_(f), or from 5.0g_(f) to 5.2 g_(f). In yet other embodiments, films may have an averagemachine direction tear from 5.2 g_(f) to 6.8 g_(f), such as from 5.4g_(f) to 6.6 g_(f), from 5.6 g_(f) to 6.4 g_(f), or from 5.8 g_(f) to6.2 g_(f). It should be understood that the above average machinedirection tear ranges include the endpoints recited therein.

In embodiments, the machine-direction oriented film has a force inmachine direction at 10% elongation—measured according to Secant ModulusASTM D 638 measured at 14 gsm—of greater than or equal to 16.0 Newtons(N), such as greater than or equal to 16.2 N, greater than or equal to16.4 N, greater than or equal to 16.6 N, greater than or equal to 16.8N, greater than or equal to 17.0 N, greater than or equal to 17.2 N,greater than or equal to 17.4 N, greater than or equal to 17.6 N, orgreater than or equal to 17.8 N. In embodiments, the machine-directionoriented film has a force at 10% elongation from 16.0 N to 18.0 N, suchas from 16.2 N to 18.0 N, from 16.4 N to 18.0 N, from 16.6 N to 18.0 N,from 16.8 N to 18.0 N, from 17.0 N to 18.0 N, from 17.2 N to 18.0 N,from 17.4 N to 18.0 N, from 17.6 N to 18.0 N, or from 17.8 N to 18.0 N.In other embodiments, the machine-direction oriented film has a force at10% elongation from 16.0 N to 17.8 N, such as from 16.0 N to 17.6 N,from 16.0 N to 17.4 N, from 16.0 N to 17.2 N, from 16.0 N to 17.0 N,from 16.0 N to 16.8 N, from 16.0 N to 16.6 N, from 16.0 N to 16.4 N, orfrom 16.0 N to 16.2 N. In yet other embodiments, the machine-directionoriented film has a force at 10% elongation from 16.2 N to 17.8 N, suchas from 16.4 N to 17.6 N, from 16.6 N to 17.4 N, or from 16.8 N to 17.2N. It should be understood that the above force at 10% elongation rangesinclude the endpoints recited therein.

Machine-direction oriented films according to embodiments may have anaverage water vapor transmission rate (WVTR)—according to ASTM D6701measured at 14 gsm, 100% relative humidity (RH), and 38° C.—of greaterthan or equal to 15,000 gram per square meter per day (g/m²/day), suchas greater than or equal to 15,250 g/m²/day, greater than or equal to15,500 g/m²/day, greater than or equal to 15,750 g/m²/day, greater thanor equal to 16,000 g/m²/day, greater than or equal to 16,250 g/m²/day,greater than or equal to 16,500 g/m²/day, or greater than or equal to16,750 g/m²/day. In embodiments, machine-oriented films may have anaverage WVTR from 15,000 to 17,000 g/m²/day, such as from 15,250 to17,000 g/m²/day, from 15,500 to 17,000 g/m²/day, from 15,750 to 17,000g/m²/day, from 16,000 to 17,000 g/m²/day, from 16,250 to 17,000g/m²/day, from 16,500 to 17,000 g/m²/day, or from 16,750 to 17,000g/m²/day. In other embodiments, machine-oriented films may have anaverage WVTR from 15,000 to 16,750 g/m²/day, such as from 15,000 to16,500 g/m²/day, from 15,000 to 16,250 g/m²/day, from 15,000 to 16,000g/m²/day, from 15,000 to 15,750 g/m²/day, from 15,000 to 15,500g/m²/day, or from 15,000 to 15,250 g/m²/day. In still other embodiments,machine-oriented films may have an average WVTR from 15,250 to 16,750g/m²/day, such as from 15,500 to 16,500 g/m²/day, or from 15,750 to16,250 g/m²/day. It should be understood that the above average WVTRranges include the endpoints recited therein.

According to embodiments, machine-direction oriented films may have ahydrostatic pressure measured according to ISO 1420—at 14 gsm greaterthan or equal to 120 centimeters (cm) water, such as greater than orequal to 121 cm water, greater than or equal to 122 cm water, greaterthan or equal to 123 cm water, greater than or equal to 124 cm water,greater than or equal to 125 cm water, greater than or equal to 126 cmwater, greater than or equal to 127 cm water, greater than or equal to128 cm water, or greater than or equal to 129 cm water. In embodiments,machine-direction oriented films have a hydrostatic pressure from 120 to130 cm water, such as from 121 to 130 cm water, from 122 to 130 cmwater, from 123 to 130 cm water, from 124 to 130 cm water, from 125 to130 cm water, from 126 to 130 cm water, from 127 to 130 cm water, from128 to 130 cm water, or from 129 to 130 cm water. In other embodiments,machine-direction oriented films have a hydrostatic pressure from 120 to129 cm water, such as from 120 to 128 cm water, from 120 to 127 cmwater, from 120 to 126 cm water, from 120 to 125 cm water, from 120 to124 cm water, from 120 to 123 cm water, from 120 to 122 cm water, orfrom 120 to 121 cm water. In still other embodiments, machine-directionoriented films have a hydrostatic pressure from 121 to 129 cm water,such as from 122 to 128 cm water, from 123 to 127 cm water, or from 124to 126 cm water. It should be understood that the above hydrostaticpressure ranges include the endpoints recited therein.

According to embodiments, machine-direction oriented films may have anoise response in Sones measured according to method described below—at18 gsm less than or equal to 5.9 Sones, less than or equal to 5.8 Sones,less than or equal to 5.7 Sones, less than or equal to 5.6 Sones, lessthan or equal to 5.5 Sones, less than or equal to 5.4 Sones, less thanor equal to 5.3 Sones, less than or equal to 5.2 Sones, less than orequal to 5.1 Sones, less than or equal to 5.0 Sones, less than or equalto 4.9 Sones. In embodiments, machine-direction oriented films may havea noise level from 4.9 Sones to 5.7 Sones, such as from 5.0 Sones to 5.7Sones, such as from 5.1 Sones to 5.7 Sones, such as from 5.2 Sones to5.7 Sones, such as from 5.3 Sones to 5.7 Sones, such as from 5.4 Sonesto 5.7 Sones, such as from 5.5 Sones to 5.7 Sones, such as from 5.6Sones to 5.7 Sones. In still other embodiments, machine-directionoriented films may have a noise level from 4.9 Sones to 5.6 Sones, suchas from 4.9 Sones to 5.5 Sones, such as from 4.9 Sones to 5.4 Sones,such as from 4.9 Sones to 5.3 Sones, such as from 4.9 Sones to 5.2Sones, such as from 4.9 Sones to 5.1 Sones, such as from 4.9 Sones to5.0 Sones. It should be understood that the above noise ranges includethe endpoints recited therein.

Films as disclosed and described herein may be used as breathablebacksheets for end products, such as, for example, infant and childdiapers, child overnight products, adult continence products, femininehygiene products, bandages, etc.

Test Methods

The testing methods include the following:

Melt index (I₂) and (I₁₀)

Melt index (I₂) values for the ethylene-based polymers measured inaccordance to ASTM D1238 at 190° C. at 2.16 kg. Similarly, melt index(Iio) values for the ethylene-based polymers were measured in accordanceto ASTM D1238 at 190° C. at 10 kg. The values are reported in g/10 min,which corresponds to grams eluted per 10 minutes.

Density

Density measurements for the ethylene-based polymers were made inaccordance with ASTM D792, Method B.

Conventional Gel Permeation Chromatography (Conventional GPC)

The chromatographic system consisted of a PolymerChar GPC-IR (Valencia,Spain) high temperature GPC chromatograph equipped with an internal IRSinfra-red detector (IRS). The autosampler oven compartment was set at160° C. and the column compartment was set at 150° C. The columns usedwere 4 Agilent “Mixed A” 30 cm 20-micron linear mixed-bed columns. Thechromatographic solvent used was 1,2,4 trichlorobenzene and contained200 ppm of butylated hydroxytoluene (BHT). The solvent source wasnitrogen sparged. The injection volume used was 200 microliters and theflow rate was 1.0 milliliters/minute.

Calibration of the GPC column set was performed with at least 20 narrowmolecular weight distribution polystyrene standards with molecularweights ranging from 580 to 8,400,000 g/mol and were arranged in 6“cocktail” mixtures with at least a decade of separation betweenindividual molecular weights. The standards were purchased from AgilentTechnologies. The polystyrene standards were prepared at 0.025 grams in50 milliliters of solvent for molecular weights equal to or greater than1,000,000 g/mol, and 0.05 grams in 50 milliliters of solvent formolecular weights less than 1,000,000 g/mol. The polystyrene standardswere dissolved at 80° C. with gentle agitation for 30 minutes. Thepolystyrene standard peak molecular weights were converted toethylene-based polymer molecular weights using the Equation 1 (asdescribed in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621(1968)):

M _(polyethylene) =A×(M _(polystyrene))^(B)  (Equation 1)

where M is the molecular weight, A has a value of 0.4315 and B is equalto 1.0.

A fifth order polynomial was used to fit the respective ethylene-basedpolymer-equivalent calibration points. A small adjustment to A (fromapproximately 0.39 to 0.44) was made to correct for column resolutionand band-broadening effects such that NIST standard NBS 1475 is obtainedat a molecular weight of 52,000 g/mol.

The total plate count of the GPC column set was performed with Eicosane(prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20minutes with gentle agitation). The plate count (Equation 2) andsymmetry (Equation 3) were measured on a 200 microliter injectionaccording to the following equations:

$\begin{matrix}{{{Plate}\mspace{14mu}{Count}} = {5.54 \times \left( \frac{{RV}_{{Peak}\mspace{14mu}{Max}}}{{Peak}\mspace{14mu}{Width}\mspace{14mu}{at}\mspace{14mu}{half}\mspace{14mu}{height}} \right)^{2}}} & \left( {{Equation}\mspace{14mu} 2} \right)\end{matrix}$

where RV is the retention volume in milliliters, the peak width is inmilliliters, the peak max is the maximum height of the peak, and halfheight is one half of the height of the peak maximum.

$\begin{matrix}{{Symmetry} = \frac{\left( {{{Rear}\mspace{14mu}{Peak}\mspace{14mu}{RV}_{{one}\mspace{14mu}{tenth}\mspace{14mu}{height}}} - {RV}_{{Peak}\mspace{14mu}\max}} \right)}{\left( {{RV}_{{Peak}\mspace{14mu}\max} - {{Front}\mspace{14mu}{Peak}\mspace{14mu}{RV}_{{one}\mspace{14mu}{tenth}\mspace{14mu}{height}}}} \right)}} & \left( {{Equation}\mspace{14mu} 3} \right)\end{matrix}$

where RV is the retention volume in milliliters and the peak width is inmilliliters, Peak max is the maximum position of the peak, one tenthheight is one tenth of the height of the peak maximum, and where rearpeak refers to the peak tail at later retention volumes than the peakmax and where front peak refers to the peak front at earlier retentionvolumes than the peak max. The plate count for the chromatographicsystem should be greater than 22,000 and symmetry should be between 0.98and 1.22.

Samples were prepared in a semi-automatic manner with the PolymerChar“Instrument Control” Software, wherein the samples were weight-targetedat 2 mg/ml, and the solvent (contained 200 ppm BHT) was added to a prenitrogen-sparged septa-capped vial, via the PolymerChar high temperatureautosampler. The samples were dissolved for 3 hours at 160° C. under“low speed” shaking.

The calculations of M_(n(GPC)), M_(w(GPC)), and M_(z(GPC)) were based onGPC results using the internal IRS detector (measurement channel) of thePolymerChar GPC-IR chromatograph according to Equations 4-7, usingPolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram ateach equally-spaced data collection point i (IR_(i)) and theethylene-based polymer equivalent molecular weight obtained from thenarrow standard calibration curve for the point i (M_(polyethylene,i) ing/mol) from Equation 1. Subsequently, a GPC molecular weightdistribution (GPC-MWD) plot (wt_(GPC)(lg MW) vs. lg MW plot, wherewt_(GPC)(lg MW) is the weight fraction of ethylene-based polymermolecules with a molecular weight of lg MW) for the ethylene-basedpolymer sample can be obtained. Molecular weight is in g/mol andwt_(GPC)(lg MW) follows the Equation 4.

∫wt _(GPC)(lg MW)d lg MW=1.00  (Equation 4)

Number-average molecular weight M_(n(GPC)), weight-average molecularweight M_(w(GPC)) and z-average molecular weight M_(z(GPC)) can becalculated as the following equations.

$\begin{matrix}{{Mn}_{({GPC})} = \frac{\sum\limits^{i}{IR}_{i}}{\sum\limits^{i}\left( {{IR}_{i}/M_{{polyethylene},_{i}}} \right)}} & \left( {{Equation}\mspace{14mu} 5} \right) \\{{Mw}_{({GPC})} = \frac{\sum\limits^{i}\left( {{IR}_{i}*M_{{polyethylene},_{i}}} \right)}{\sum\limits^{i}{IR}_{i}}} & \left( {{Equation}\mspace{14mu} 6} \right) \\{{Mz}_{({GPC})} = \frac{\sum\limits^{i}\left( {{IR}_{i}*{M_{{polyethylene}_{,i}}}^{2}} \right)}{\sum\limits^{i}\left( {{IR}_{i}*M_{{polyethylene},_{i}}} \right)}} & \left( {{Equation}\mspace{14mu} 7} \right)\end{matrix}$

In order to monitor the deviations over time, a flow rate marker(decane) was introduced into each sample via a micropump controlled withthe PolymerChar GPC-IR system. This flow rate marker (FM) was used tolinearly correct the pump flow rate (Flowrate(nominal)) for each sampleby RV alignment of the respective decane peak within the sample (RV(FMSample)) to that of the decane peak within the narrow standardscalibration (RV(FM Calibrated)). Any changes in the time of the decanemarker peak are then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run. To facilitate the highestaccuracy of a RV measurement of the flow marker peak, a least-squaresfitting routine is used to fit the peak of the flow marker concentrationchromatogram to a quadratic equation. The first derivative of thequadratic equation is then used to solve for the true peak position.After calibrating the system based on a flow marker peak, the effectiveflow rate (with respect to the narrow standards calibration) iscalculated as Equation 8. Processing of the flow marker peak was donevia the PolymerChar GPCOne™ Software. Acceptable flow rate correction issuch that the effective flowrate should be within 0.5% of the nominalflowrate.

Flow rate_(effective)=Flow rate_(nominal)×(RV(FM _(calibrated))/RV(FM_(Sample)))  (Equation 8)

Crystallization Elution Fractionation (CEF)

Comonomer distribution analysis, also commonly called short chainbranching distribution (SCBD), is measured with Crystallization ElutionFractionation (CEF) (PolymerChar, Spain) (Monrabal et al, Macromol.Symp. 257, 71-79 (2007), which is incorporated herein by reference inits entirety) equipped with an IR (IR-4 or IR-5) detector (PolymerChar,Spain) and 2-angle light scattering detector Model 2040 (PrecisionDetectors, currently Agilent Technologies). Distilled anhydrousortho-dichlorobenzene (ODCB) with 600 ppm antioxidant butylatedhydroxytoluene (BHT) was used as solvent. For the autosampler with thecapability of N₂ purge, no BHT was added. A GPC guard column (20microns, or 10 microns, 50×7.5 mm) (Agilent Technologies) is installedjust before the IR detector in the detector oven. Sample preparation isdone with an autosampler at 160° C. for 2 hours under shaking at 4 mg/ml(unless otherwise specified). The injection volume is 300 μl. Thetemperature profile of CEF is: crystallization at 3° C./min from 110° C.to 30° C., the thermal equilibrium at 30° C. for 5 minutes, elution at3° C./min from 30° C. to 140° C. The flow rate during crystallizationwas at 0.052 ml/min. The flow rate during elution is at 0.50 ml/min. Thedata was collected at one data point/second.

The CEF column is packed by The Dow Chemical Company with glass beads at125 μm±6% (MO-SCI Specialty Products) with ⅛-inch stainless tubing.Glass beads are acid washed by MO-SCI Specialty by request from The DowChemical Company. Column volume is 2.06 ml. Column temperaturecalibration was performed by using a mixture of NIST Standard ReferenceMaterial Linear ethylene-based polymer 1475a (1.0 mg/ml) and Eicosane (2mg/ml) in ODCB. Temperature was calibrated by adjusting elution heatingrate so that NIST linear ethylene-based polymer 1475a has a peaktemperature at 101.0° C., and Eicosane has a peak temperature of 30.0°C. The CEF column resolution was calculated with a mixture of NISTlinear ethylene-based polymer 1475a (1.0 mg/ml) and hexacontane (Fluka,purum≥97.0%, 1 mg/ml). A baseline separation of hexacontane and NISTethylene-based polymer 1475a was achieved. The area of hexacontane (from35.0 to 67.0° C.) to the area of NIST 1475a from 67.0 to 110.0° C. is 50to 50, the amount of soluble fraction below 35.0° C. is less than 1.8wt. %. The CEF column resolution is defined in Equation 9:

$\begin{matrix}{{Resolution} = {\frac{\begin{matrix}{{{Peak}\mspace{14mu}{Temperature}_{{NIST}\mspace{14mu} 1475A}} -} \\{{Peak}\mspace{14mu}{Temperature}_{Hexacontane}}\end{matrix}}{\begin{matrix}{{{Width}\mspace{14mu}{at}\mspace{14mu}{Half}\mspace{14mu}{Height}_{{NIST}\mspace{14mu} 1475A}} +} \\{{Width}\mspace{14mu}{at}\mspace{14mu}{Half}\mspace{14mu}{Height}_{Hexacontane}}\end{matrix}} \geq 6.0}} & \left( {{Equation}\mspace{14mu} 9} \right)\end{matrix}$

where the half height width is measured in temperature and resolution isat least 6.0.

Short Chain Branching Distribution (SCBD)—CEF Full Width at Half Height

An additional parameter to describe the short chain branchingdistribution is the CEF full width at half height. This is done by theprocedure outlined below:

(A) Obtain a weight fraction at each temperature (T) (w_(T)(T)) from20.0° C. to 119.0° C. with a temperature step increase of 0.20° C. fromCEF according to the following equation:

∫_(20.0) ^(119.0) w _(T)(T)dT=1, and  (Equation 13)

(B) Obtain maximum peak height from CEF comonomer distribution profileby searching each data point for the highest peak from 35.0° C. to119.0° C. The SCBD CEF full width at half height is defined as theentire temperature difference between the front temperature and the reartemperature at the half of the maximum peak height. The fronttemperature at the half of the maximum peak is searched forward from35.0° C., and is the first data point that is greater than or equal tohalf of the maximum peak height. The rear temperature at the half of themaximum peak is searched backward from 119.0° C., and is the first datapoint that is greater than or equal to half of the maximum peak height.

The high density fraction (HDF) can be calculated as an integral fromthe CEF curve from 93° C. to 119° C. This is defined as the integral ofthe IR-4 chromatogram (baseline subtracted measurement channel) in theelution temperature ranging from 93° C. to 119° C. divided by the totalintegral from 20° C. to 140° C. according to the following equation:

$\begin{matrix}{{HDF} = {\frac{\int_{93.0}^{119.0}{IRdT}}{\int_{20.0}^{140.0}{IRdT}}*100\%}} & \left( {{Equation}\mspace{14mu} 14} \right)\end{matrix}$

where T is the elution temperature (from the calibration discussedabove).

Zero-Shear Viscosity Ratio (ZSVR)

Zero-shear viscosity ratio is defined as the ratio of the zero-shearviscosity (ZSV) of the branched polyethylene material to the ZSV of alinear polyethylene material (see ANTEC proceeding below) at theequivalent weight average molecular weight in g/mol (M_(w(GPC))),according to the following Equation 15:

$\begin{matrix}{{ZSVR} = {\frac{\eta_{0B}}{\eta_{0L}} = {\frac{\eta_{0B}}{2.29 \times 10^{- 15}{{Pa} \cdot \sec \cdot \left( \frac{g}{mol} \right)^{- 3.65}} \times M_{w{({GPC})}}^{3.65}}.}}} & \left( {{Equation}\mspace{14mu} 15} \right)\end{matrix}$

The ZSV value of the LLDPE based polymer (η_(0B)) was obtained fromcreep test, at 190° C., via the method described below. The M_(w(GPC))value was determined by the conventional GPC method (Equation 6), asdiscussed above. The correlation between ZSV of linear polyethylene(η_(0L)) and its M_(W)(GPC) was established based on a series of linearpolyethylene reference materials. A description for the ZSV-M_(w(GPC))relationship can be found in the ANTEC proceeding: Karjala et al.,Detection of Low Levels of Long-chain Branching in Polyolefins, AnnualTechnical Conference—Society of Plastics Engineers (2008), 66^(th)887-891.

Creep Test

The ZSV value of the LLDPE polymer (η_(0B)) was obtained from a constantstress rheometer creep test at 190° C. in a nitrogen environment usingDHR, TA Instrument. The LLDPE samples were subjected to flow between two25 mm diameter plate fixtures positioned parallel to each other. Sampleswere prepared by compression molding pellets of LLDPE into circularplaques of about 1.5-2.0 mm thick. The plaques were further cut into 25mm diameter disks and sandwiched between the plate fixtures of the TAInstrument. The oven on the TA instrument was closed for 5 minutes aftersample loading and before setting the gap between the plate fixtures to1.5 mm, opening the oven to trim the edges of the sample, and reclosingthe oven. A logarithmic frequency sweep between 0.1 to 100radians/second at 190° C., 300 seconds of soak time, and 10% strain wasconducted before and after the creep test to determine whether thesample degraded. A constant low shear stress of 20 Pa was applied forall of the samples, to ensure that the steady state shear rate was lowenough to be in the Newtonian region. Steady state was determined bytaking a linear regression for the data in the last 10% time window ofthe plot of “lg(J(t)) vs. lg(t)”, where J(t) was creep compliance and twas creep time. If the slope of the linear regression was greater than0.97, steady state was considered to be reached, then the creep test wasstopped. In all cases in this study, the slope meets the criterionwithin one hour. The steady state shear rate was determined from theslope of the linear regression of all of the data points, in the last10% time window of the plot of “c vs. t”, where c was strain. Thezero-shear viscosity was determined from the ratio of the applied stressto the steady state shear rate.

Machine-Direction Orientation Tear

Tear in machine direction was measured according to Elmendorf Tear ASTMD 1922 measured at 14 gsm. An average value of 15 specimens werereported.

Machine-Direction Force at 10% Elongation

Force in machine direction at 10% elongation was measured according toASTM D 638. Rectangular film samples were cut along the machinedirection with a 1 inch wide and 6 inches long. The grip-to-gripdistance was 4 inches. Samples were stretched to 15% elongation with anInstron tensile machine at a tensile speed of 20 inch/minute. The forceat 10% elongation was recorded. An average value of 5 specimens werereported.

Water Vapor Transmission Rate (WVTR)

WVTR was measured according to ASTM D 6701 measured at 14 gsm, 100%relative humidity, and 38° C. using a Mocon PERMATRAN-W 101K. An averagevalue of 6 specimens were reported.

Hydrostatic Pressure

Hydrostatic pressure was measured according to ISO 1420 measured at 14gsm. An average value of 3 specimens were reported.

Noise Measurement

A test setup as shown in FIG. 3A and FIG. 3B is designed to measure andquantify the noise. In particular, FIG. 3A shows a film 300 positionedbetween two supports 310 a, 310 b, and the supports 310 a, 310 b aremoved in the direction show by the arrows to laterally stretch the film300. FIG. 3B shows a test set up where three microphones 320 a, 320 b,320 c are positioned about 2 inches to 3 inches away from the film whileit is being stretched to record the noise. To avoid the influence ofbackground noise on sample measurements, the tests are conducted in ananechoic chamber that has low ambient noise floor as given Table 1below. Film samples of size 10×20 cm are cut from film rolls andmeasured. One of the long side of the film sample is locked verticallyto prevent movement and the opposite, free end, is actuated along thevertical axes as shown by double-sided red arrow in below Figure (at arate of 1 Hz). The noise generated is captured by three microphones(placed at a distance of 6 cm from the specimen) as shown in belowFigure. Data acquisition and post processing is done using industrystandard B&K software and hardware; actuation is done for 20 [sec] at asampling rate of 32.768 [kHz] and the data is post-processed to evaluatethe loudness in Sones. The test is repeated three times andaverage/standard deviation of the runs are reported.

TABLE 1 Octave band (Hz) SPL, dB 125 33.8 250 23.3 500 17.7 1000 18.92000 10.7 4000 11.5 8000 12.9

EXAMPLES

The following examples illustrate features of the present disclosure butare not intended to limit the scope of the disclosure.

Example 1

An ethylene-based polymer was formed using a loop reactor as the firstreactor and a plug flow reactor as the second reactor. The feed streaminto the first reactor included 1327 pounds per hour (lb/hr) ISOPAR-Esolvent, 186 lb/hr ethylene monomer, 25 lb/hr octene. Hydrogen was alsointroduced into the first reactor at 6200 sccm. The first reactor exitethylene concentration was 17 g/L. The first catalyst introduced intothe first reactor included a procatalyst and a cocatalyst. Theprocatalyst was zirconium,dimethyl[[2,2′″-[[bis[1-methylethyl)germylene]bis(methyleneoxy-κO)]bis[3″,5,5″-tris(1,1-dimethylethyl)-5′-octyl[1,1′:3′,1″-terphenyl]-2′-olato-κO]](2-)]having the following structure:

The procatalyst was added as needed to control 17 g/L reactor exitethylene concentration and procatalyst loading was typically 0.80 μmonin the reactor exit. The cocatalysts were bis(hydrogenated tallowalkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine andtriethylaluminum.

The first reactor was heated to a temperature of 190° C. and theethylene monomer and octene reacted in the presence of the firstcatalyst to form a first polymer fraction.

A second catalyst was added to the effluent downstream from the firstreactor and upstream from the second reactor to form a modifiedeffluent. The second catalyst was a Ziegler-Natta catalyst at aconcentration of about 1.9 μmon. The modified effluent was introducedinto the second, plug flow reactor where the unreacted ethylene and theunreacted octene and unreacted hydrogen reacted in the presence of thesecond catalyst to form a second polymer fraction.

The bimodal ethylene-based polymer produced in the foregoing examplecomprised 91.7 wt. % first polymer fraction, 8.3 wt. % second polymerfraction measured using traditional modeling of ethylene consumption inthe first and second reactors. The bimodal ethylene-based polymer had amelt index (I₂) of 3.56 g/10 min, a density of 0.9154 g/cc, and anI₁₀/I₂ ratio of 5.75, each measured in accordance with the techniquesdisclosed previously.

Example 1 and Comparative Examples 1-5

Example 1 comprises: a combination of 45 wt % LLDPE, the type of whichas indicated in Table 1 as Resin 1; 5 wt % AGILITY™ EC 7000 manufacturedby The Dow Chemical Company as the LDPE component; and 50 wt % CaCO₃Filmlink™ 500 manufactured by Imerys as the pore former. Details arereported in Table 2.

Comparative Examples 1-5 comprise: a combination of 45 wt % LLDPE, thetype of which as indicated in Table 1 as Comparative Resin 1-4; 5 wt %AGILITY™ EC 7000 manufactured by The Dow Chemical Company as the LDPEcomponent; and 50 wt % CaCO₃ Filmlink™ 500 manufactured by Imerys as thepore former. Details are reported in Table 2.

Examples 2 and 3 comprise: a combination of 50 wt % LLDPE, the type ofwhich as indicated in Table 1 as Resin 1; and 50 wt % CaCO₃ Filmlink™500 manufactured by Imerys as the pore former. Details are reported inTable 3.

Comparative Examples 6-10 comprise: a combination of 50 wt % LLDPE, thetype of which as indicated in Table 1 as Comparative Resin 1, 3 and 4;and 50 wt % CaCO₃ Filmlink™ 500 manufactured by Imerys as the poreformer. Details are reported in Table 3.

DOWLEX™ 2047G and ELITE™ 5220 G are manufactured by The Dow ChemicalCompany, and EXCEED™ 3518CB is manufactured by the ExxonMobilCorporation. The composition of the LLDPE of comparative Example 5 isdescribed in WO 2017/152065, which is incorporated by reference hereinin its entirety. Properties of the LLDPE based polymers are shown inTable 2 below.

TABLE 2 SCBD width HDFby at half I₂ Density CEF height by (g/10 min)I₁₀/I₂ (g/cm³) ZSVR (%) CEF (° C.) Resin: Example 1 3.6 5.8 0.915 1.594.6 6.8 Comparative resin 2.3 7.5 0.920 1.20 19.3 31.8 1: DOWLEX ™ 2047GComparative resin 3.5 6.7 0.915 1.83 10.9 9.2 2: ELITE ™ 5220GComparative resin 3.5 5.6 0.918 1.10 4.7 15.6 3: EXCEED ™ 3518CBComparative resin 3.6 6.8 0.920 2.49 1.0 4.2 4: Example 5 ofWO2017/152065

For Example 1 and Comparative Examples 1-5 the ethylene-based polymer,AGILITY™ EC 7000, and Filmlink™ 500 CaCO₃ were compounded on a CoperionZSK 26 twin screw extruder. Barrel length was 100 mm per with 15 barrelscomprising the entire process section. Screw diameter was 25.5 mm with aflight depth of 4.55 mm. The screw design used was the General PurposeScrew. The residence time of material was controlled by the screwdesign, feed rate of 25 lbs./hr., and a screw RPM of 400. No oil wasinjected. There was no side arm feeder. For Example 1 and ComparativeExamples 1-5, the ethylene-based polymer and Agility™ EC 7000 pelletswere dry blended by drum rotation in a ratio of 90:10 by weight prior tobeing fed directly into the main feed throat of the ZSK26 by a K-Tron,T-20, LWF, K-11 feeder. The Filmlink™ 500 CaCO₃ was simultaneously fedinto the main feed throat of the ZSK 26 by a K-Tron, T-20, LWF, K-7feeder with powder screw and fluffer installed. The K-7 feeder and K-11feeder operated such that 50 wt % blend: 50 wt % CaCO₃ was delivered tothe ZSK 26. Nitrogen was also fed into the feed throat adapter at 5 SCFHto sweep drop pipe which brings the material to the extruder. Zone 2temperature was 115° C., Zone 3 was 190° C., and Zone 4-15 and dieextruder temperature was 200° C. There was no vacuum pulled. Thecompounded material was sent through a water bath after exiting theZSK-26 and before being cut by a strand cut pelletizer. Aftercollection, the pelletized materials were nitrogen purged and sealed inair tight bags. After the product was packaged it was sent off to aseparate laboratory for film extrusion, stretching, and testing.

For Example 2-3 and Comparative Examples 6-10 the ethylene-basedpolymer, and Filmlink™ 500 CaCO₃ were compounded on a BUSS CompounderMDK/E 46 (BUSS S.A. Basel, Switzerland). Compounding conditions aresummarized in Table 3 below. Each of the resulting compounds were driedfor six hours at 60° C. and then packed in aluminum bags to avoidmoisture pick-up before extrusion.

TABLE 3 Kneading ASV T screw T Z1 T Z2 T ASV T DIE speed speed DIECutter (° C.) (° C.) (° C.) (° C.) (° C.) (rpm) (rpm) dimensions speed(n) 110 130 135 130 135 110 60 3 5

Monolayer, machine direction-oriented (MDO) films were produced from allthe above combination on a Collin cast MDO line as follows. MDO filmswere fabricated using a Collin cast MDO line. The Collin cast MDO lineis equipped with a cast film unit and an online MDO unit. The cast filmunit has three extruders (25/30/25 mm) and a slot die (0.7 mm die gap).Monolayer cast films are first produced with the cast film unit at athroughput rate of 2 kg/h. The films are quenched on a chill roll (chillroll temperature=20° C.) in the cast film unit before entering theonline MDO unit. The preheat roll temperature in the online MDO unit isset at a temperature that is 15° C. lower than the draw temperature (orstretch temperature). Stretch temperature was 60° C. The film isstretched in machine direction in the MDO unit and the machine directionorientation ratios (or stretch ratios) of the MDO films are shown inTable 2 and Table 3. Final film thickness (after MDO) for Example 1 andComparative Examples 1-5 is fixed at 14 GSM. Final film thickness (afterMDO) for Examples 2-3 and Comparative Examples 6-10 is fixed at 18 GSM.

Machine direction orientation ratio was measured as ratio of thevelocity of the film existing the MDO unit to the velocity of the filmentering the MDO unit.

The properties of the film comprising the resin of Example 1 and thefilms comprising the resins of Comparative Examples 1 to 5, which wereformed according to the above methods are shown below in Table 4.

TABLE 4 Force in machine Machine WVTR-Avg- Average direction atDirection Transmission Hydrostatic machine 10% Orientation Rate pressuredirection elongation Example Composition Ratio (g/m²/day) (cm Water)Tear (g_(f)) (Newtons) Film 1 45 wt % Example 1 5.6x 16418 125 5.3 16 5wt % AGILITY ™ EC 7000 50 wt % CaCO₃ Comp. Film 1 45 wt % DOWLEX ™ 5.3x6746 115 4.8 12.3 2047G 5 wt % AGILITY ™ EC 7000 50 wt % CaCO₃ Comp.Film 2 45 wt % DOWLEX ™ 5.8x 7416 126 4.9 18.9 2047G 5 wt % AGILITY ™ EC7000 50 wt % CaCO₃ Comp. Film 3 45 wt % ELITE ™ 5.8x 9770 114 4.3 11.65220G 5 wt % AGILITY ™ EC 7000 50 wt % CaCO₃ Comp. Film 4 45 wt %EXCEED ™ 4.0x 12350 110 4.7 14.6 3518CB 5 wt % AGILITY ™ EC 7000 50 wt %CaCO₃ Comp. Film 5 45 wt % Example 5 of 5.3x 20830 96 4.0 15.9WO2017/152065 5 wt % AGILITY ™ EC 7000 50 wt % CaCO₃

As can be seen in Table 4 the film according to Example 1 has a betterbalance of machine direction tear, machine direction force at 10%elongation, WVTR, and hydrostatic pressure than the films according toComparative Examples 1-5. These results are graphically depicted in FIG.2, which shows hydrostatic pressure results (in cm water) of Example 1and Comparative Examples 1-5 on the positive x-axis, machine directiontear results (in g_(f)) of Example 1 and Comparative Examples 1-5 on thenegative y-axis, machine direction force at 10% strain results (inNewtons) of Example 1 and Comparative Examples 1-5 on the negativex-axis, and WVTR results (in g/m²/day) of Example 1 and ComparativeExamples 1-5 on the positive y-axis.

As can be seen from the examples and comparative examples, films madeaccording to embodiments disclosed and described herein provide improvedoverall balance of properties. For instance, Comparative Example 5 has ahigher WVTR value than Example 1, but Example 1 outperforms ComparativeExample 1 in hydrostatic pressure and average machine direction tear.Similarly, Comparative Example 2 has the highest force in machinedirection at 10% elongation of the example and comparative examples, butExample 1 outperforms Comparative Example 2 in all other measuredcategories. Accordingly, each of the comparative examples targets highperformance of a certain property at the expense of other properties,but Example 1 provides values for each measured property at or near themaximum value achieved by any one of the comparative examples. Thus, thefilm of example 1 provides a better overall film than any of thecomparative examples.

TABLE 5 Machine Direction Orientation Noise Example Composition Ratio(Sones) Ex. 2 50 wt % Example 1 5.1x 5.7 50 wt % CaCO₃ Comp. Ex. 6 50 wt% DOWLEX ™ 2047G 5.2x 5.9 50 wt % CaCO₃ Comp. Ex. 9 50 wt % Example 5 of5.2x 6.9 WO2017/152065 50 wt % CaCO₃ Ex. 3 50 wt % Example 1 5.8x 6.0 50wt % CaCO₃ Comp. Ex. 7 50 wt % DOWLEX ™ 2047G 5.8x 6.3 50 wt % CaCO₃Comp. Ex. 8 50 wt % EXCEED ™ 3518CB 5.7x 7.1 50 wt % CaCO₃ Comp. Ex. 1050 wt % Example 5 of 5.7x 7.9 WO2017/152065 50 wt % CaCO₃

As can be seen in Table 5, at same machine direction orientation ratio,Examples 2-3 outperform Comparative Examples 6-10 when it comes toloudness as measured. The improvement in loudness is irrespective of themachine direction orientation ratio used.

It will be apparent that modifications and variations are possiblewithout departing from the scope of the disclosure defined in theappended claims. More specifically, although some aspects of the presentdisclosure are identified herein as preferred or particularlyadvantageous, it is contemplated that the present disclosure is notnecessarily limited to these aspects. Additionally, all ranges recitedin this disclosure include the endpoints of the ranges unlessspecifically state otherwise (such as by “less than” or “greater than”).

1. A film comprising: 20.0 weight percent to 69.5 weight percent linearlow density polyethylene (LLDPE) based polymer, wherein the LLDPE basedpolymer comprises a high density fraction (HDF) from 3.0% to 8.0%,wherein the high density fraction is measured by crystallization elutionfractionation (CEF) integration at temperatures from 93° C. to 119° C.,an I₁₀/I₂ ratio from 5.5 to 6.9, wherein I₂ is the melt index whenmeasured according to ASTM D 1238 at a load of 2.16 kg and temperatureof 190° C. and I₁₀ is the melt index when measured according to ASTM D1238 at a load of 10 kg and temperature of 190° C., and a short chainbranching distribution (SCBD) of less than or equal to 8.0° C., whereinthe short chain branching distribution is measured by CEF full width athalf height; 0.0 weight percent to 10.0 weight percent low densitypolyethylene (LDPE) based polymer; and 30.0 weight percent to 70.0weight percent pore former.
 2. A film according to claim 1, wherein thefilm comprises from 40.0 weight percent to 60.0 weight percent LLDPEbased polymer.
 3. A film according to claim 1, wherein the LLDPE basedpolymer has a zero shear viscosity ratio from 1.1 to 3.0.
 4. A filmaccording to claim 1, wherein the LLDPE based polymer has a I₁₀/I₂ ratiofrom 5.5 to 6.5.
 5. A film according to claim 1, wherein the LLDPE basedpolymer has a density of 0.910 to 0.925 g/cm³, wherein density ismeasured according to ASTM D792, Method B.
 6. A film according to claim1, wherein the LLDPE based polymer has an 12 from 1.0 to 6.0 g/10 mins,wherein 12 is measured according to ASTM D 1238 at a load of 2.16 kg. 7.A film according to claim 1, wherein the LLDPE based polymer has an 12from 3.0 to 4.0 g/10 mins.
 8. A film according to claim 1, wherein thefilm is a machine-direction oriented film.
 9. A film according to claim8, wherein the film has a machine-direction orientation ratio from 2.5×to 6.0×, wherein machine-direction orientation ratio is calculated asratio of the velocity of the film existing the MDO unit to the velocityof the film entering the MDO unit
 10. A film according to claim 1,wherein the film has an average machine-direction tear greater than orequal to 5.0 g_(f), wherein the average machine-direction tear ismeasured according to Elmendorf Tear ASTM D 1922 measured at 14 gsm. 11.A film according to claim 1, wherein the film has an averagemachine-direction force at 10% elongation of greater than or equal to16.0 Newtons, wherein average machine-direction force at 10% elongationis measured according to ASTM D 638 at a tensile speed of 20 inch/minuteand measured at 14 gsm.
 12. A film according to claim 1, wherein thefilm has an average water vapor transmission rate of greater than orequal to 15,000 g/m²/day wherein average water vapor transmission rateis measured according to ASTM D6701 measured at 14 gsm, 100% RH, and 38°C.
 13. A film according to claim 1, wherein the film has a hydrostaticpressure of greater than or equal to 120 cm water, wherein thehydrostatic pressure is measured according to ISO 1420 measured at 14gsm.
 14. A film according to claim 1, wherein the film has a loudness ofless than 5.9 sones, wherein the loudness is measured at 18 gsm and amachine direction orientation ratio of less than or equal to 5.2×, orthe film has a loudness of less than 6.3 sones, wherein the loudness ismeasured at 18 gsm and a machine direction orientation ratio greaterthan 5.2× and less than or equal to 5.8×.
 15. A hygiene absorbentproduct comprising the film according to claim 1.